CN1217824A - Copolymers of vinylidene fluoride and hexafluoropropllene having reduced extractable content and improved solution clarity - Google Patents

Copolymers of vinylidene fluoride and hexafluoropropllene having reduced extractable content and improved solution clarity Download PDF

Info

Publication number
CN1217824A
CN1217824A CN199898800207A CN98800207A CN1217824A CN 1217824 A CN1217824 A CN 1217824A CN 199898800207 A CN199898800207 A CN 199898800207A CN 98800207 A CN98800207 A CN 98800207A CN 1217824 A CN1217824 A CN 1217824A
Authority
CN
China
Prior art keywords
copolymer
hfp
vinylidene fluoride
weight
vdf
Prior art date
Application number
CN199898800207A
Other languages
Chinese (zh)
Other versions
CN1311577C (en
Inventor
R·A·威尔
M·T·伯奇尔
Original Assignee
北美埃尔夫爱托化学股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US3834697P priority Critical
Priority to US3101598A priority
Application filed by 北美埃尔夫爱托化学股份有限公司 filed Critical 北美埃尔夫爱托化学股份有限公司
Priority to PCT/US1998/004071 priority patent/WO1998038687A1/en
Publication of CN1217824A publication Critical patent/CN1217824A/en
Application granted granted Critical
Publication of CN1311577C publication Critical patent/CN1311577C/en

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565Polymeric materials, e.g. gel-type or solid-type
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • H01M2/16Separators; Membranes; Diaphragms; Spacing elements characterised by the material
    • H01M2/164Separators; Membranes; Diaphragms; Spacing elements characterised by the material comprising non-fibrous material
    • H01M2/1653Organic non-fibrous material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0085Immobilising or gelification of electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders

Abstract

本发明公开了新颖的偏氟乙烯和六氟丙烯共聚物,共聚物含有最高约为24%(重量)的六氟丙烯,它比已有技术中详细描述能够再现的合成方法制得的HFP含量相同的偏氟乙烯-六氟丙烯共聚物有改善的溶液透明性和流动性、较长的胶凝时间和减少的可萃取量,含有这些共聚物的材料的新组成和制品。 The present invention discloses a novel vinylidene fluoride and hexafluoropropylene, copolymers of hexafluoropropylene containing up to about 24% (by weight), which is described in greater detail than in the prior art can be reproduced in the synthetic methods of HFP content same vinylidene fluoride - hexafluoropropylene copolymer solution has improved transparency and flowability, long gel time and reduced amount of extractables, the composition and articles containing the novel copolymers of these materials. 还公开了根据本发明的新的偏氟乙烯/六氟丙烯共聚物、有双峰型分子量分布的偏氟乙烯均聚物和单体分布基本均匀的偏氟乙烯/三氟氯乙烯共聚物的新的电池结构。 Also discloses a new invention of vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride with a bimodal molecular weight distribution homopolymer and a substantially uniform distribution of monomers vinylidene fluoride / chlorotrifluoroethylene copolymer the new cell structure.

Description

可萃取量减少、溶液透明性改善的偏氟乙烯和六氟丙烯共聚物 The amount of extraction can be reduced, improving the transparency of the solution of vinylidene fluoride and hexafluoropropylene copolymer

本申请要求了1997年2月28日提交的临时申请No.60/038,346的优先权。 This application claims the provisional application February 28, 1997 filed No.60 / 038,346 of.

发明的背景本发明涉及化学领域中的含氟聚合物类组合物,具体涉及偏氟乙烯(VDF)的共聚物,更具体地涉及偏氟乙烯和六氟丙烯(HFP)的共聚物,尤其具体涉及可萃取量减少、胶凝时间延长和溶液透明性改善的VDF和HFP的共聚物,含有这些共聚物的材料的新组成和制品,以及共聚物、含有这些共聚物制品的组分及制品的制备和应用方法。 Background of the Invention The present invention relates to a fluorine-containing polymer-based composition in the chemical field, particularly relates to a copolymer of vinylidene fluoride (VDF), and more particularly, to a copolymer of vinylidene fluoride and hexafluoropropylene (HFP), and in particular the specific relates to the amount of extraction can be reduced, and the gel time was extended improved transparency VDF and HFP copolymers, copolymers containing these new material compositions and articles, and copolymers, copolymers containing these products and components of products preparation and application methods.

VDF/FHP共聚物是人们所熟知的,它们由于有热塑性工程(thermoplasticengineering)性能、耐化学性和耐降解性而被使用。 VDF / FHP copolymers are well known, because they are thermoplastic engineering (thermoplasticengineering) properties, chemical resistance and resistance to degradation is used. 它们可用于,例如耐化学管道、垫片、充气电缆护套、滤膜和萃取膜以及用于锂电池的结构中。 They can be used, for example, chemical-resistant pipes, gaskets, pneumatic cable sheathing, membranes and films, and a structure for the extraction of the lithium battery.

本发明提供了含有最高约24%(重量)(12%(摩尔))HFP的VDF/HFP共聚物,它有改善的性能、基本上改进的溶液透明性、较长的胶凝时间和减少的可萃取量(这些术语在下文中有所描述)。 The present invention provides a HFP VDF / HFP copolymer contains up to about 24% (by weight) (12% (mol)), it has improved performance, substantially improved the transparency of a solution, a longer gel time and reduced extractable amount (these terms are described below).

用于制备本发明共聚物的方法中需要确定初始加入反应器的VDF/HFP比值和随后连续加入单体时的VDF/HFP的不同比值。 A method for preparing the copolymer of the present invention is determined initially added to the reactor VDF / HFP and VDF ratio is then continuously added at a monomer / HFP of different ratios. 共聚物制品中任何特别要求的HFP平均含量与特定的初始加料比和随后加料比相对应。 The average content of HFP copolymer products with special requirements of any particular ratio of the initial charge and then charging ratio corresponds. 与已有技术所述的VDF/HFP共聚物相比,用这种方法制得的组成的均匀性提供了独特而有用的性能。 Compared with the prior art VDF / HFP copolymer, the uniformity obtained by this method a composition provides a unique and useful properties.

本发明也提供了从本发明的VDF/HFP共聚物制得的锂电池,以及从下文描述的其它均聚物和共聚物制得的锂电池,这些均聚物和共聚物用已知的方法制得并有类似的结构,本发明发明者认为它们有类似于本发明VDF/HFP共聚物的加工性能,这使得它们特别适用于锂电池的结构中。 The present invention also provides the present invention from the VDF / HFP copolymers prepared lithium batteries, and other homopolymers and copolymers prepared from the following description of the lithium battery, these homopolymers and copolymers by known methods prepared and have a similar structure, the present inventors believe that they have similar processing properties of the present invention, VDF / HFP copolymer, which makes them particularly suitable for the structure of the lithium battery.

已有技术的描述Rexord在美国专利No.3,051,677中描述了HFP含量为30-70%(重量)(15-50%(摩尔))的VDF/HFP共聚物,它可用作弹性体。 Rexord described prior art describes HFP content is 30-70% (by weight) (15-50% (mol)) of the VDF / HFP copolymers in U.S. Patent No.3,051,677, which can be used as an elastomer. 该文描述了用VDF和HFP有一定初始比的间歇生产方法,和在整个过程中VDF和HFP有固定比值的连续方法来制备共聚物。 The described method of producing a batch VDF and HFP with a certain initial ratio of VDF and HFP and has a continuous process in a fixed ratio throughout the process to prepare the copolymer. 所述的方法制得的聚合物没有本发明的改善的溶液透明性、较长的胶凝时间和减少的可萃取量。 The method of the resulting polymer solution is not improved transparency of the present invention, a longer gel time and reduced amount of extractable.

Lo在美国专利No.3,178,399中描述了HFP含量为2-26%(重量)(1-13%(摩尔))的VDF/HFP共聚物,该产物有拉伸强度(psig)值,可逆伸长率至少为1,000,000。 Lo in U.S. Patent No.3,178,399 is described in the HFP content of 2-26% (wt) (1-13% (mol)) of the VDF / HFP copolymer, the product has a tensile strength (psig) value, reversibly elongatable of at least 1,000,000. 它采用VDF和HFP初始比一定的间歇方法,或是在整个过程中VDF和HFP比值固定的半连续方法来制备共聚物。 It uses a batch method of VDF and HFP certain initial ratio, or the ratio of VDF and HFP fixed semi-continuous process for preparing copolymers in the whole process. 所述的方法制得的共聚物没有本发明共聚物的改善的溶液透明性、较长的胶凝时间和减少的可萃取量。 The copolymer prepared by the method was not improved transparency copolymer of the present invention, longer gel time and reduced amount of extractable.

Moggi等在Polymer Bulletin 7,115-122(1982)中通过核磁共振和X射线衍射试验分析了VDF/HFP共聚物的微结构和晶体结构。 Moggi et analyzed VDF / HFP microstructure and crystal structure of the copolymer by nuclear magnetic resonance and X-ray diffraction test was Polymer Bulletin 7,115-122 (1982) in. 最高含31%(重量)(最高为16%(摩尔))HFP的共聚物是用间歇乳液法制得的,该方法在转化率很低的情况下进行。 Containing up to 31% (by weight) (up to 16% (mole)) HFP copolymers are obtained by a batch emulsion legal, the process is carried out at a low conversion conditions. 尽管低转化率的间歇法可以制得溶液透明的和可萃取量低的共聚物,但是该文中没有描述这些性质。 Despite the low conversion batch process can be obtained solution was clear and low weight copolymer can be extracted, but this article does not describe these properties. 它并不是适用于工业的实用方法,因为制得材料所要求的转化率很低。 It is not suitable for practical industrial method, because of the low to obtain the desired conversion material. 另外,该文也没有提供详细的聚合反应实例。 Also, this article does not provide a detailed example of the polymerization reaction.

Bonardelli等在Polymer Vol.27,905-909(1986年6月)中研究了HFP含量高达62%(重量)(41%(摩尔))的VDF/HFP共聚物的玻璃化温度。 Bonardelli other studies HFP content up to 62% (by weight) (41% (mol)) of VDF in Polymer Vol.27,905-909 (1986 June 2011) / HFP copolymer glass transition temperature. 玻璃化温度与共聚物中HFP总含量相关。 The glass transition temperature associated with the total content of HFP copolymers. 在制备共聚物进行分析时,采用了半连续乳液法,该方法采用了不同的初始加入反应器的VDF/HFP比值和随后连续加入单体的VDF/HFP比值。 In the preparation of the copolymer are analyzed using a semi-continuous emulsion process, which uses a different initial VDF added to the reactor / HFP ratio and then continuously adding monomers VDF / HFP ratios. 尽管参照采用竞聚率设定初始加料的VDF/HFP比,但是该文没有提供详细的聚合反应实例,而且也没有提到制得的共聚物有与本发明共聚物类似的溶液透明性、胶凝时间和减少的可萃取量。 While the use of reference reactivity ratio setting initial charge of VDF / HFP ratio, but this article does not provide detailed examples of the polymerization reaction, but there is no mention of the obtained copolymer with a copolymer solution of the present invention similar to the transparency, adhesive coagulation time and reduce the amount of extractable.

Pianca等在Polymer,vol.28,224-230(1987年2月)中用核磁共振测定了VDF/HFP共聚物的微结构,并用微结构测定结果来解释共聚物玻璃化温度的趋势。 Pianca et Polymer, vol.28,224-230 (1987 February 2009) measured by NMR microstructure of the VDF / HFP copolymer, and the measurement result is explained by the microstructure tendency of the glass transition temperature of the copolymer. 共聚物的合成使用一种半连续乳液法,该方法采用了不同的初始加入反应器的VDF/HFP比值和随后连续加入单体的VDF/HFP比值。 Synthesized using a semi-continuous emulsion copolymer, the method uses different initial VDF added to the reactor / HFP and VDF ratio is then continuously added to the monomer / HFP ratio. 该文没有提供详细的合成实例,也没有提到共聚物有本发明共聚物提供的改善的溶液透明性、较长的胶凝时间和减少的可萃取量。 The paper does not provide detailed examples of the synthesis, there was no mention of the transparency of the copolymer is the copolymer of the present invention provides an improved, longer gel time and reduced amount of extractable.

Abusleme等在欧洲专利申请No.650,982 A1中揭示了制备氟化烯烃和任选的一种或多种非氟化烯烃的聚合物和共聚物的乳液法。 Abusleme etc. In European Patent Application No.650,982 A1 discloses emulsion polymers and copolymers prepared fluorinated olefin and optionally one or more non-fluorinated olefins. 该方法依靠光化学引发聚合反应,这样可使用比热引发方法所用更低的温度和压力。 The method relies on a photochemical polymerization initiator, it may be used so that the specific heat initiation temperature and lower pressure method used. 尽管该文大致描述了制得的聚合物的结构规则性,但是只提到了与聚偏氟乙烯有关的规则性,而且没有对组成的规则性提出权利要求。 Although this paper describes a substantially regular structure of the polymer prepared, but only mentioned regularity associated with polyvinylidene fluoride, and made no claim to the regularity thereof. 该文给出了VDF/HFP共聚反应的实例,但没有描述共聚物的溶液萃取性能,而且也没有指出VDF/HFP共聚物的物理性能和结构之间的关系。 In this paper, the VDF / HFP copolymerization of Example, but does not describe the properties of the copolymer solution was extracted, and does not indicate the relationship between the structure and the physical properties of the VDF / HFP copolymer.

Morgan在美国专利No.5,543,217中揭示了用一种半连续乳液法制得的均匀的四氟乙烯/六氟丙烯共聚物(TFE/HFP共聚物)。 Morgan discloses a semi-continuous emulsion obtained by uniformly SYSTEM tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP copolymer) in U.S. Patent No.5,543,217 in. 均匀性简单地定义为聚合物链中有低比例的相邻HFP单元;另外该文没有揭示TFE和HFP单元的排列,也没有提到VDF/HFP共聚物或从该文预计到的性能。 Simply defined as the uniformity of the polymer chain has a low proportion of an adjacent HFP units; Further this article does not disclose TFE and HFP units are arranged, there is no mention VDF / HFP copolymers to paper or expected from the performance.

这些对比文献均没有提到一种获得VDF/HFP共聚物的方法,该共聚物有与本发明VDF/HFP共聚物或从VDF/HFP共聚物可获得的性质相当的溶液透明性和流动性、较长的胶凝时间和减少的可萃取量。 These references are not mentioned method of a VDF / HFP copolymer is obtained, the copolymer of the present invention has the VDF / HFP copolymer, or from the nature of VDF / HFP copolymer was obtained in comparable transparency and flowability, longer gel time and reduced amount of extractable.

美国专利4,076,929在其分子权利要求中描述了有均匀分布的较多缺陷结构的VDF均聚物的合成方法。 U.S. Patent No. 4,076,929 synthetic methods defect structure has more uniform distribution of VDF homopolymer in its molecule described in the claims.

美国专利2,752,331描述了合成VDF/三氟氯乙烯(CTFE)共聚物的方法,该共聚物在其分子权利要求中有高度均匀的共聚单体分布。 U.S. Patent No. 2,752,331 describes the synthesis of VDF / chlorotrifluoroethylene (CTFE) copolymers, which copolymers have a highly uniform comonomer distribution in its molecule claims.

Baggett和Smith在High Polymers,Vol.ⅩⅧ,Ham,John Wiley(1964),Chapter Ⅹ,Copolymerization,pp.587以及以后等,(尤其是pp.593和610)中描述了偏氯乙烯和氯乙烯以及氯乙烯和乙酸乙烯酯的均匀组成分布共聚物的合成方法。 Baggett and Smith, High Polymers, Vol.ⅩⅧ, Ham, John Wiley (1964), Chapter Ⅹ, etc. Copolymerization, pp.587 and beyond, (especially pp.593 and 610) are described as well as vinylidene chloride and vinyl chloride vinyl chloride and vinyl acetate uniform composition distribution of the copolymer synthesis process.

美国专利5,296,318指出,只有HFP含量为8-25%(重量)的VDF/HFP共聚物适于用来制造锂电池电极和隔片,而其它VDF的均聚物或共聚物是不适宜的。 U.S. Patent No. 5,296,318 points out that only the HFP content is 8-25% (by weight) of the VDF / HFP copolymers suitable for use in manufacturing a lithium battery separator and electrode, and the other of VDF homopolymer or copolymer is undesirable.

美国专利5,348,818指出,在其它聚合物中,VDF聚合物可用来制成二次电池制造中所用的固体电解质。 U.S. Patent No. 5,348,818 points out, in other polymers, polymers can be made of VDF solid-electrolyte secondary battery used in the manufacture. 但没有指出具体类型的聚偏氟乙烯及其任何类型的共聚物。 But not which particular type of polyvinylidene fluoride and copolymers of any type.

欧洲专利申请95 120 660.6-1215(1996年9月4日出版)指出在锂电池中采用约7-25%共聚单体含量的微孔(开孔或闭孔)VDF共聚物和采用VDF均聚物作为用于这些电池的覆盖材料。 European Patent Application No. 95 120 660.6-1215 (September 4, 1996 published) said microporous about 7-25% comonomer content (open or closed cell) in a lithium battery and a copolymer of VDF VDF homopolymerization using It was used as covering materials for these batteries. 该文没有指出将本发明所用共聚物用于固体电解质,也没有指出其提供的改进的性能。 The article does not indicate the copolymers of the present invention is used for a solid electrolyte, but also does not indicate which provide improved performance. 同样也没有指出本发明所用的VDF均聚物可用于固体电解质。 Also no indication used in the present invention may be used homopolymers of VDF solid electrolyte.

这些对比文献均没有提到本发明采用的摇椅式锂电池,而美国专利5,296,318特别指出不能使用任何类型的VDF均聚物、HFP含量小于8%(重量)的VDF/HFP共聚物或其它含有VDF的共聚物。 These references are not mentioned rocking chair type lithium battery of the present invention is employed, and particularly pointed out in U.S. Patent No. 5,296,318 does not use any type of homopolymer of VDF, HFP content of less than 8% (by weight) of the VDF / HFP copolymer or VDF containing other copolymers.

美国专利5,571,634提到了采用共聚物中CTFE含量不低于8%(重量)的VDF-CTFE共聚物来制造锂离子电池。 U.S. Patent No. 5,571,634 mentions using VDF-CTFE copolymer CTFE copolymer containing not less than 8% (by weight) to manufacture a lithium ion battery.

发明概述本发明第一方面提供了一种偏氟乙烯和六氟丙烯的共聚物,该共聚物含有最高约为24%(重量)的六氟丙烯,其溶液有改善的透明性和流动性;对于HFP标称含量最高约为8%(重量)的共聚物,它的可萃取物重量百分数在通过选自下式a)%(重量)可萃取物=1.7(HFP%(摩尔))-3.2b)%(重量)可萃取物=-1.2+1.5(HFP%(摩尔))-8×10-6(Mn)计算出的可萃取物重量百分比的±1.5%范围内,对于HFP标称含量大于约8%(重量)的共聚物,其DSC(差示扫描量热法)熔点比用已有技术中详细描述的方法制得的HFP标称含量相同的共聚物DSC熔点至少低2.5℃。 Summary of the first aspect of the present invention provides a copolymer of vinylidene fluoride and hexafluoropropylene, hexafluoropropylene copolymer containing up to about 24% (by weight), which was transparent and improved flowability; for HFP copolymer nominal content of up to about 8% (by weight), which weight percent extractables by a formula selected from a)% (wt) extractables = 1.7 (HFP% (mole)) - 3.2 b)% (wt) extractables = + 1.5 ((-1.2 HFP% by mole)) - in the range of ± 1.5% 8 × 10-6 (Mn) can be calculated by weight of the extract, for the nominal HFP content copolymer greater than about 8% (by weight), the DSC (differential scanning calorimetry) melting point of the same than with the prior art method described in detail in the nominal HFP content of the resulting copolymer is low DSC melting point of at least 2.5 ℃.

本发明第一方面的明确实例是草黄色至无色的半结晶固体,该固体的熔点(经差示扫描量热法(DSC)测得)比用已有技术中详细报道的方法制得的HFP标称百分含量相同的VDF/HFP共聚物低。 Clear example of a first aspect of the present invention is a colorless to straw-colored semi-crystalline solid, the melting point of the solid (by differential scanning calorimetry (DSC) as measured) than the prior art method reported in detail prepared same percentage of the nominal VDF HFP / HFP copolymer low.

本发明第一方面的明确实例从溶液胶凝的时间比用已有技术中详细报道的方法制得的HFP标称含量相同的VDF/HFP共聚物更长。 Examples clear from a first aspect of the present invention, the gelling time of the solution than with the same method reported in detail in the prior art prepared nominal HFP content of the copolymer of VDF HFP longer /.

将前述物理性质和合成方法结合在一起考虑,必然能确定该结构和找出可申请专利的组成的新颖性。 The method of synthesis and the physical properties considered together, must be able to determine the structure and composition find novel and patentable.

本发明第一方面的明确实例有特有的用途,它适于用作油漆和粉末涂料载体和有载体或无载体的耐化学的成形物体和膜。 Clear example of a first aspect of the invention has a specific purpose, it is suitable for use as films and molded objects paints and powder coatings and carriers supported or unsupported chemical resistance. 特别提到的是含有约2-8%(重量)HFP的本发明第一方面的共聚物,更特别的是含有约3-6%(重量)HFP的共聚物,它有特有的用途,特别适于用作电池用,尤其是锂电池用聚合物隔片和聚合物电极基材。 Specifically mentioned is a copolymer of a first aspect of the present invention contain from about 2-8% (by weight) of HFP, more particularly about 3-6% (wt.) HFP containing copolymer, which has unique applications, especially suitable for use as a battery, especially a lithium battery separator and a polymer electrolyte polymer substrate.

已有技术(参见例如美国专利5,296,318)已经报道了用含8-25%(重量)HFP的VDF/HFP共聚物制得的锂电池。 Prior art (see, e.g. U.S. Pat. No. 5,296,318) has been reported containing 8-25% (by weight) of HFP VDF / HFP copolymers prepared lithium battery. 应当理解,HFP含量在该范围内的本发明共聚物也适用于这些电池,并表现出有所改进。 It will be appreciated, the content of HFP copolymers of the invention in this range also apply to these cells, and exhibits improved. 这些改进的电池也被考虑作为本发明的等价物。 These modified cells are also contemplated as equivalents of the present invention.

特别指出的是含有约7-15%(重量)HFP的本发明第一方面的共聚物,尤其是含有约10%(重量)HFP的共聚物,它有适于用作电线和电缆的阻燃绝热材料的特有用途。 Of particular note is a copolymer of a first aspect of the present invention contain from about 7-15% (by weight) of HFP, particularly those containing from about 10% (by weight) HFP copolymer which is suitable as a flame retardant wire and cable specific use of the insulating material.

还提到的是含有大于约15%(重量)HFP的本发明第一方面的共聚物,尤其是含有约16%(重量)或更高的HFP的共聚物,它有用作透明、柔软的耐化学性薄膜的特有用途。 Also it is mentioned that contains greater than about 15% (by weight) of the HFP copolymer of the first aspect of the present invention, especially those containing from about 16% (by weight) or higher HFP copolymer, which has as a transparent, flexible resistance the use of specific chemical film.

本发明第二方面提供了一种改进的制品,该制品是电化学电池,电池有一个正极、一个吸收剂隔片和一个负极,其中电极中的至少一个和/或所述吸收剂隔片包含结合有电解质材料的偏氟乙烯聚合物,其中改进之处包括聚偏氟乙烯聚合物基本上由选自有双峰型分子量分布的偏氟乙烯均聚物、有基本均匀的单体分布的偏氟乙烯/三氟氯乙烯共聚物和本发明第一方面确定的偏氟乙烯/六氟丙烯共聚物的偏氟乙烯聚合物组成。 A second aspect of the present invention provides an improved article, the article is an electrochemical cell, the battery has a positive electrode, a separator and a negative electrode absorber, wherein the at least one electrode and / or the absorbent sheet comprises a separator electrolyte material combined with vinylidene fluoride polymer, wherein the improvement comprises polyvinylidene fluoride with a polymer selected from the group consisting essentially of vinylidene fluoride bimodal molecular weight distribution homopolymer, biased substantially uniform distribution of the monomers vinyl fluoride / chlorotrifluoroethylene copolymer and a first aspect of the present invention determines the vinylidene fluoride / hexafluoropropylene copolymer, a vinylidene fluoride polymer.

特别提到的本发明第二方面的实例是六氟丙烯含量约为2-8%(重量)、尤其是3-6%(重量)、更特别的是约为3%(重量)的VDF/HFP共聚物。 Examples of the second aspect of the present invention is specifically mentioned hexafluoropropylene content of about (by weight) 2-8%, particularly 3-6% (by weight), more particularly about 3% (by weight) of the VDF / HFP copolymer.

有双峰型分子量分布的偏氟乙烯均聚物指如美国专利4,076,729所述制得的偏氟乙烯均聚物。 Bimodal molecular weight distribution means a vinylidene fluoride homopolymer of vinylidene fluoride as described in U.S. Patent No. prepared the homopolymer 4,076,729.

单体分布基本上均匀的偏氟乙烯/三氟氯乙烯共聚物指如美国专利2,751,331所述制得的偏氟乙烯/三氟氯乙烯共聚物。 A substantially uniform distribution of monomers vinylidene fluoride / chlorotrifluoroethylene copolymer as described in U.S. Patent No. 2,751,331 refers to the obtained vinylidene fluoride / chlorotrifluoroethylene copolymer.

特别提到的是CTFE含量约为2-8%(重量)的VDF/CTFE共聚物,更特别的是CTFE含量约为3-6%(重量)的VDF/CTFE共聚物。 Specifically mentioned CTFE content of about 2-8% (by weight) of the VDF / CTFE copolymer, more particularly a VDF / CTFE copolymer CTFE content of about 3-6% (by weight) of.

如本文和所附的权利要求书中所用的,本发明的偏氟乙烯聚合物(或VDF聚合物)指如上确定的有双峰型分子量分布的聚偏氟乙烯均聚物、如上确定的单体分布基本上均匀的VDF/CTFE共聚物和/或本发明第一方面的VDF/HFP共聚物。 As used herein and claimed in the appended claims, the vinylidene fluoride of the present invention, ethylene polymer (or polymeric VDF) means as defined bimodal molecular weight distribution of a homopolymer of polyvinylidene fluoride, as determined by single a substantially uniform distribution of body VDF / CTFE copolymer and / or the first aspect of the present invention, VDF / HFP copolymers.

本发明第二方面的电化学电池是PCT申请WO 95/06332、欧洲专利申请95120 660.6-1215(1996年9月4日以730,316 A1公布号出版)和美国专利5,296,318中所述的电池改进方案。 A second aspect of the present invention is an electrochemical cell PCT Application WO 95/06332, European Patent Application No. 95 120 660.6-1215 (September 4, 1996 to Publishing Publication No. 730,316 A1) and U.S. Patent No. 5,296,318 in the development of a battery. PCT申请、欧洲申请和美国专利中揭示的内容均结合入本文作参考。 PCT Application, U.S. Patent and European application disclosed contents of which are incorporated herein by reference.

除了采用前述对比文献中所述的溶液浇铸方法来制备用于电池结构中的膜外,还考虑采用挤塑方法来制备这些膜和从膜制得电池。 Cell structure of the film except that the comparative solution casting method described in the literature to prepare for the outside, is also contemplated to prepare these films and films prepared from the cells obtained using the extrusion process.

也应注意,与从已有技术的VDF-HFP共聚物制得的电池相比,从上述VDF聚合物,尤其是本发明的VDF-HFP共聚物制得的电池的聚合物和电极金属部分间的粘合性更佳,使用温度更高。 Note also that, compared with the obtained between the VDF-HFP copolymer manufactured by prior art battery, from the VDF polymers, in particular made of VDF-HFP copolymer obtained by the present invention and a polymer battery electrode metal portions better adhesion, higher temperature. 也观察到,与已有技术的VDF-HFP共聚物制得的电池相比,本发明的VDF-HFP共聚物提供了电性能改善(如放电率更高)的电池。 Also observed, as compared with VDF-HFP copolymer prepared by prior art battery, VDF-HFP copolymer according to the present invention provide improved electrical performance (e.g., higher discharge rate) of the battery. 本发明发明者可以预计,根据本发明制得的电池通常具有较高的使用温度和较高的放电率。 The inventors of the present invention can be expected, in accordance with the present invention was prepared cells typically have a higher temperature and a higher discharge rate.

本发明第三方面提供了本发明第一方面的组合物的溶液,该溶液有改进的溶液透明性和流动性。 A third aspect of the present invention provides a solution composition of the first aspect of the present invention, the solution was improved transparency and flowability.

六氟丙烯含量最高约为24%(重量)的偏氟乙烯和六氟丙烯的共聚物是有用的半结晶热塑性塑料。 A copolymer of vinylidene fluoride and hexafluoropropylene, hexafluoropropylene content of up to about 24% (by weight) are useful semicrystalline thermoplastic. 随着材料中HFP含量的增加,结晶度降低,因此柔韧性和溶剂敏感性增加。 With increasing HFP content in the material, the degree of crystallinity decreases, thus increasing the flexibility and sensitivity of the solvent. 其它性质也发生变化,例如最终熔点,它随着HFP含量的增加而减少。 Other properties are also changed, for example, a final melting point, which increases as HFP content decreases. 在高纯度应用,如膜过滤或萃取、制造锂电池、用溶液浇铸制备高透明性的膜以及要求污染很少的流体储藏和运输中,希望材料有低含量的可萃取物,在溶剂存在下几乎不形成凝胶,和有良好的透明性。 In high-purity applications, such as membrane filtration or extraction to produce a lithium battery, high transparency of the film prepared by solution casting, and requires little contaminated fluid storage and transport, the desirable material has a low content of extractables, in the presence of a solvent hardly form a gel, and has good transparency. 与已有技术制得的HFP含量相同的非均匀VDF/HFP共聚物相比,本发明提供的VDF/HFP共聚物有减少的可萃取量、改进的溶液性质、改进的透明性和流动性以及较低的熔点。 HFP content compared with the prior art made of the same non-uniformity of the VDF / HFP copolymers, provided by the present invention of VDF / HFP copolymer may be a decrease in the amount of extracted, improved solution properties, improved transparency and flowability and lower melting point.

附图描述图1显示了本发明共聚物和合成方法已有详细描述的已有技术化合物的差示扫描量热法熔点(DSC熔点)的最终比较结果。 DESCRIPTION OF THE DRAWINGS FIG. 1 shows the final result of the comparison differential scanning calorimetry melting point of the compounds of the prior art and the present invention copolymer synthesis methods have been described in detail (DSC melting point) is.

图2显示了在碳酸二甲酯(DMC)中40℃下本发明共聚物和合成方法已有详细描述的已有技术共聚物中HFP含量对聚合物可萃取物的影响。 Figure 2 shows the effect of the HFP content of the polymer extractables in the prior art copolymers of dimethyl carbonate (DMC) at 40 ℃ copolymers and synthetic methods of the present invention have been described in detail.

图3显示了本发明共聚物和合成方法详细描述可再现的已有技术共聚物中HFP含量与从共聚物溶液(20%(重量),在碳酸亚丙酯中)胶凝时间对数值的关系。 Figure 3 shows a prior art copolymers and synthetic copolymers of the present invention may be methods described in detail in the reproduced HFP content (20% (by weight) in propylene carbonate) from the relationship between values ​​copolymer solution gel time .

图4是根据本发明的电化学电池的剖面图。 FIG 4 is a sectional view of an electrochemical cell according to the invention.

详细描述本发明提供了六氟丙烯含量最高约为24%(重量)且有改进的溶液透明性、流动性和较少的可萃取物的偏氟乙烯和六氟丙烯共聚物。 DETAILED DESCRIPTION The present invention provides a hexafluoropropylene content of up to about 24% (by weight) solution and an improved transparency, vinylidene fluoride and hexafluoropropylene copolymer flowability and less extractables. 共聚物可通过乳液聚合反应方法来方便地制得,但是也可采用悬浮法和溶液法。 Copolymers by emulsion polymerization method may be conveniently prepared, but suspension and solution processes may be employed. 在乳液聚合反应方法中,在反应器中加入去离子水、可在聚合反应时乳化反应物的水溶性表面活性剂、石蜡防污剂、偏氟乙烯、六氟丙烯、控制共聚物分子量的链转移剂和引发并维持聚合反应的引发剂。 In the emulsion polymerization process, deionized water in a reactor, the water-soluble surfactant emulsion reactant, paraffin antifoulant, vinylidene fluoride, hexafluoropropylene during the polymerization reaction, the molecular weight of the control chain of the copolymer transfer agent and initiator and maintain the polymerization initiator. 为了获得本发明的VDF/HFP共聚物,VDF和HFP单体的初始加料量是HFP含量最高为初始加入的单体总重量的48%,然后再整个反应期间连续加入VDF和HFP,使得HFP含量最高为持续加入单体总重量的24%。 In order to obtain the present invention VDF / HFP copolymers, VDF and HFP initial feeding quantity monomers are HFP content of up to 48% of the total weight of the monomers initially charged, and then added continuously throughout the reaction period VDF and HFP, the HFP content such that continuously added up to 24% of the total weight of the monomers. 初始加料时的VDF/HFP比和连续加料时的不同,每种最终聚合物组成均有确定的相对应的初始加料比和连续加料比。 And continuously feeding at different time of initial charge VDF / HFP ratios are determined for each of the final polymer composition corresponding to the ratio of the initial charge and feed ratio continuously. 该方法中VDF和HFP单体的总用量是HFP的用量最高约为单体总重量的24%。 The total amount of the process VDF and HFP monomers are HFP in an amount up to about 24% of the total weight of the monomers.

反应器是装有搅拌器和加热控制装置的加压聚合反应器。 The reactor was equipped with a stirrer and a heating control means pressurized polymerization reactor. 聚合反应的温度可根据采用的引发剂的性质而不同,但是它通常在65-105℃,更方便地是在75-95℃。 The polymerization temperature may be the nature of the initiator used is different, but it is usually at 65-105 deg.] C, more conveniently at 75-95 ℃. 然而,温度不局限于上述范围,如果采用高温或低温引发剂,温度可以更高或更低。 However, the temperature range is not limited to the above, if high or low temperature initiator, the temperature may be higher or lower. 聚合反应中所用的VDF/HFP比值由反应所选温度来确定。 The polymerization reaction is used in the VDF / HFP ratios determined by the selected reaction temperature. 聚合反应的压力通常在2750-6900kPa,但是如果设备允许在更高的压力下进行操作的话,压力也可以更高。 Polymerization pressure is usually 2750-6900kPa, but if the equipment permits operation at higher pressure, then the pressure may be higher. 最合适的压力在3790-5860kPa。 The most appropriate pressure 3790-5860kPa.

聚合反应中所用的表面活性剂是水溶性的卤化表面活性剂,尤其是氟化表面活性剂,如全氟化或部分氟化的烷基羧酸的铵盐、取代的铵盐、季铵盐或碱金属盐;全氟化或部分氟化的单烷基磷酸酯;全氟化或部分氟化的烷基醚或聚醚羧酸盐;全氟化或部分氟化的烷基磺酸盐和全氟化或部分氟化的烷基硫酸盐。 Surfactants used in the polymerization are water-soluble surface active halogenating agents, in particular fluorinated surfactants, alkyl ammonium salts of carboxylic acids, such perfluorinated or partially fluorinated, substituted ammonium, quaternary ammonium or alkali metal salts; perfluorinated or partially fluorinated monoalkyl phosphate; alkyl sulfonates perfluorinated or partially fluorinated; perfluorinated or partially fluorinated alkyl ether or polyether carboxylates and perfluorinated or partially fluorinated alkyl sulfates. 一些具体的非限制性例子是美国专利No.2,559,752中描述的酸的盐,其结构式为X(CF2)nCOOM,其中X是氢或氟,M是碱金属、铵、取代的铵(如有1-4个碳原子的烷基胺)、季铵离子,n是6-20间的整数;硫酸的聚氟链烷醇酯,其结构式为X(CF2)nCH2OSO3M,其中X和M如上所述;以及结构式为CF3(CF2)n(CX2)mSO3M的盐,其中X和M如上所述,n是3-7之间的整数,m是0-2间的整数,如全氟辛基磺酸钾。 Some specific non-limiting examples are acid salts described in U.S. Patent No.2,559,752, having the formula X (CF2) nCOOM, wherein X is hydrogen or fluorine, M is an alkali metal, ammonium, substituted ammonium (if 1 alkylamine to 4 carbon atoms), a quaternary ammonium ion, n being an integer between 6-20; polyfluoro alkanol esters of sulfuric acid, having the formula X (CF2) nCH2OSO3M, wherein X and M are as described above; and salts of the formula CF3 (CF2) n (CX2) mSO3M, where X and m are as described above, n being an integer between 3-7, m is an integer between 0-2, such as perfluorooctyl sulfonic acid potassium . 表面活性剂的加入量为所用单体总重量的0.05-2%(重量),更佳的为0.1-0.2%(重量)。 The amount of surfactant added is from 0.05 to 2% (by weight) of the total weight of the monomers used, it is better (by weight) 0.1-0.2%.

石蜡防污剂是常规的,可采用任何长链饱和烃蜡或油。 Paraffin is a conventional antifoulant, any long chain saturated hydrocarbon wax or oil. 石蜡加入反应器的量为所用单体总重量的0.01-0.3%(重量)。 Paraffin is added to the reactor an amount from 0.01 to 0.3% of the total weight of the monomers used (by weight).

在将去离子水、表面活性剂和石蜡防污剂加入反应器中后,将氮气通入反应器或是抽真空以除去氧气。 After Deionized water, surfactant and paraffin antifoulant added to the reactor, nitrogen was fed into the reactor or evacuated to remove oxygen. 对反应器调温,并可任意地加入链转移剂。 The reactor temperature control, and optionally a chain transfer agent is added. 然后反应器用偏氟乙烯和六氟丙烯的混合物来加压。 The reactor was then a mixture of ethylene and vinylidene fluoride hexafluoropropylene be pressurized.

可采用的链转移剂是用于氟化单体的聚合反应的熟知的链转移剂。 Chain transfer agents may be used chain transfer agents are well known in the polymerization of fluorinated monomers. 醇、碳酸酯、酮、酯和醚是氧化的化合物,它们可用作链转移剂。 Alcohols, carbonates, ketones, esters and ethers are oxygenated compounds which are useful as chain transfer agents. 具体的非限制性实例是异丙醇(如美国专利No.4,360,652中公开的)、丙酮(如美国专利No.3,857,827中公开的)和乙酸乙酯(如出版的待审查申请公开号为JP 58065711中公开的)。 Specific non-limiting examples are isopropanol (as disclosed in U.S. Patent No.4,360,652), acetone (as disclosed in U.S. Patent No.3,857,827) and ethyl acetate (e.g., Published Unexamined Application Publication No. JP 58065711 disclosed). 其它类可用作氟化单体聚合反应中的链转移剂的化合物是卤化碳和氢卤化碳,如含氯烃、含氢氯烃、氯氟烃和氢氯氟烃;具体的非限制性实例是三氯氟甲烷(如美国专利No.4,569,978中公开的)和1,1-二氯-2,2,2-三氟乙烷。 Fluorinated monomers other classes of compounds useful as polymerization chain transfer agent in the reaction of the halogenated halocarbon carbon and hydrogen, such as chlorinated hydrocarbons, a hydrogen-containing chlorocarbons, chlorofluorocarbons and hydrochlorofluorocarbons; specific non-limiting examples of trichlorofluoromethane (as disclosed in U.S. Patent No.4,569,978), and 1,1-dichloro-2,2,2-trifluoroethane. 链转移剂可在反应开始时一次加入,在整个反应过程中分几次加入或随着反应的进行而连续加入。 The chain transfer agent may be added at the beginning of the reaction time, several additions or continuously as the reaction was added throughout the reaction carve. 链转移剂的加入量和采用的加料方式根据链转移剂的活性和所需的产物分子量特点来决定。 The amount of chain transfer agent were added and addition methods used to determine the molecular weight of the product according to the characteristics of an active chain transfer agent and the desired. 所用的链转移剂的量为所用单体总重量的0.05-5%(重量),以0.1-2%(重量)为更佳。 The amount of chain transfer agent used is from 0.05 to 5% (by weight) of the total weight of the monomers used, at 0.1 to 2% (by weight) is more preferred.

反应器通过加入确定比例(第一有效比)的偏氟乙烯和六氟丙烯单体来加压,使得六氟丙烯最高为初始加入的单体总重量的48%(重量)。 Determining the ratio of the reactor by the addition (first effective ratio) of vinylidene fluoride and hexafluoropropylene monomers is pressurized, so that the maximum hexafluoropropylene (wt) 48% by weight of the total monomers initially added. 所用的第一有效比根据两种单体在所选聚合反应温度下的相对活性来确定。 The first effective ratio is determined according to the selected relative activity in the two monomers at the reaction temperature used for the polymerization. 偏氟乙烯和六氟丙烯的活性在Bonardelli等,Poymer,vol.27,905-909(1986年6月)中已有报道。 Vinylidene fluoride and hexafluoropropylene like activity have been reported in Bonardelli, Poymer, vol.27,905-909 in (June 1986). 相对活性使得为了获得特别均匀的共聚物组成,必须在初始加料时在反应器中加入比接入共聚物中更多的六氟丙烯。 To obtain the relative activity such homogeneous copolymers in particular, must be added more than the access hexafluoropropylene copolymer in the reactor at the initial charge. 在本发明合适的聚合反应温度范围内,在初始加料时必须在反应器中加入为聚合物中含量两倍的六氟丙烯。 Within a suitable temperature range of the polymerization reaction of the present invention, the polymer must be added to the content of hexafluoropropylene twice in the reactor at the initial charge.

反应可通过加入任何适宜的已知用于氟化单体聚合反应的引发剂来引发和保持,引发剂包括无机过氧化物、氧化剂和还原剂的氧化还原组合和有机过氧化物。 The reaction by the addition of fluorinated monomers may be used any suitable known polymerization initiator used to initiate and maintain a redox initiator comprising a combination of an inorganic peroxide, an oxidizing agent and a reducing agent and an organic peroxide. 典型的无机过氧化物的实例是过硫酸的铵盐或碱金属盐,它们在65-105℃的温度范围内有活性。 Examples of typical inorganic peroxides are the ammonium or alkali metal salts of sulfuric acid, which are active in the temperature range of 65-105 deg.] C. “氧化还原”体系可在更低的温度下进行操作,其实例包括氧化剂(如过氧化氢、叔丁基过氧化氢、氢过氧化枯烯或过硫酸盐)和还原剂(如还原性金属盐(二价铁盐是具体的实例))的组合,任选地还可与活化剂(如甲醛次硫酸氢钠或抗坏血酸)组合使用。 "Redox" system may operate at lower temperatures, examples thereof include an oxidizing agent (such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or persulfate) and a reducing agent (e.g., reducing metal combination of salts (ferrous salt are specific examples)), optionally also with an activator (e.g., sodium formaldehyde sulfoxylate or ascorbic acid) in combination. 可用于聚合反应的有机过氧化物是二烷基过氧化物、过氧化酯类和过氧化二碳酸酯。 The organic peroxide may be used in the polymerization reaction are dialkyl peroxides, peroxy esters and peroxy dicarbonate. 二烷基过氧化物的实例是二叔丁基过氧化物,过氧化酯类的实例是过氧新戊酸叔丁酯和过氧新戊酸叔戊酯,过氧二碳酸酯的实例是过氧二碳酸二正丙酯、过氧二碳酸二异丙酯、过氧二碳酸二仲丁酯和过氧二碳酸(2-乙基己)酯。 Examples of dialkyl peroxides is di-t-butyl peroxide, peroxyesters examples are t-butyl peroxypivalate and t-amyl peroxypivalate, peroxydicarbonates examples are di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate and peroxy dicarbonate (2-ethylhexyl) ester. 在美国专利No.3,475,396中指出了过氧二碳酸二异丙酯在偏氟乙烯聚合反应中以及和另一种氟化单体的共聚反应中的应用,在美国专利No.4,360,652中还描述了其在制备偏氟乙烯/六氟丙烯共聚物中的应用。 Application noted copolymerization diisopropyl peroxydicarbonate in vinylidene fluoride polymerization and another fluorinated monomer and in the U.S. Patent No.3,475,396, the U.S. Patent No.4,360,652 also described application of an ethylene / hexafluoropropylene copolymer thereof in the manufacture of vinylidene fluoride. 出版的待审查申请公开号为JP 58065711中描述了过氧二碳酸二正丙酯在偏氟乙烯聚合反应中的应用。 Published Unexamined Application Publication No. JP 58065711 describes di-n-propyl peroxydicarbonate Application to the polymerization of the vinylidene fluoride. 聚合反应需要的引发剂量与引发剂的活性和聚合反应所用的温度有关。 Living polymerization initiator required dose and the polymerization initiator used in the reaction temperature. 所用的引发剂的总量通常在所用单体总重量的0.05-2.5%(重量)范围内。 The total amount of initiator used is usually within (by weight) in the range 0.05-2.5% by weight of the total monomers used. 通常,在反应开始时加入足量的引发剂来引发反应,然后可任选地加入补加的引发剂来保持聚合反应处于合适的速度下。 Typically, adding a sufficient amount at the beginning of the reaction initiator to initiate the reaction, and then optionally adding additional initiator to maintain the polymerization reaction at the appropriate speed. 引发剂可以纯物质、溶液、悬浮液或乳液的形式加入,这要根据所选的引发剂。 The initiator may be a pure substance, a solution, suspension or emulsion form is added, according to which the selected initiator. 作为一个特殊的引发剂,可以水性乳液的形式方便地加入过氧化二碳酸酯类。 As a specific initiator, in the form of aqueous emulsion may be conveniently added peroxydicarbonate esters.

随着反应的进行,以确定的比例(第二有效比)加入偏氟乙烯和六氟丙烯单体的混合物,以维持反应压力。 As the reaction proceeded, the ratio (second effective ratio) was added to a mixture of ethylene determine vinylidene fluoride and hexafluoropropylene monomers, to maintain the reaction pressure. 所用的第二有效比与最终共聚物组成中所需的单体单元比相一致,它最高可以为在整个反应过程中连续加入的单体总重量的24%。 A second monomer unit ratio of the final copolymer effectively used than is consistent, it may be up to 24% of added continuously throughout the reaction total weight of the monomers. 连续加入偏氟乙烯、六氟丙烯和任选的引发剂和链转移剂直至获得所需的反应器加料量。 Continuous addition of vinylidene fluoride, hexafluoropropylene, and optionally initiator and chain transfer agent until the desired reactor feeding quantity.

在达到所需的反应器加料量时,停止加入单体。 Upon reaching the desired reactor charging amount, the monomer was stopped. 为获得有最佳溶液透明性和最少的可萃取物的共聚物,其它进料和单体进料同时停止,并尽快使反应器排气。 To obtain a copolymer solution has the best transparency and minimal extractables, and other feed and stop the monomer feed, the reactor and the exhaust gas quickly. 或者以溶液透明性和可萃取物为代价获得最高产率,可在任意地继续加入引发剂下采用反应完全(react-out)来消耗剩余的单体。 Or a solution of extractables transparency and the highest yield of the cost, can continue to be added at any of initiator employed reaction was complete (react-out) to consume the remaining monomers. 对于反应完全,维持反应温度和搅拌20-30分钟,但是如果需要将单体消耗至反应器压力不再显著降低的话,可采用更长的时间。 For the completion of the reaction, maintaining the reaction temperature and stirred for 20-30 minutes, but if necessary the monomer to the reactor pressure is no longer consume significantly reduced, it can be longer. 在反应完全后,可采用10-40分钟的稳定时间。 After completion of the reaction, it can be 10 to 40 minutes of settling time. 在稳定期间,保温但不加入引发剂。 During steady incubated without addition of an initiator. 然后使反应器冷却并排气。 Then the reactor was cooled and vented.

产物以胶乳形式回收。 The product recovered in the form of a latex. 为了获得干的树脂,使胶乳凝结,分离凝固物,分离的凝固物可以清洗。 To obtain dry resin, the latex coagulated, the coagulum separation, the separated coagulum may be washed. 为了提供粉末,可以干燥凝固物。 To provide powder, the coagulum dried.

对于凝结步骤,可采用数种熟知的方法,包括冷冻、加入酸或盐、或在任意加热条件下的机械剪切。 For the coagulation step, several well-known methods may be employed, including freezing, addition of an acid or a salt thereof, or any mechanical shearing under heating conditions. 如果需要,粉末还可加工制成粒料或其它合适的树脂形态。 If desired, the powder can be processed into pellets or other suitable form of resins.

本发明的电化学电池是基于操作时相互毗连的正极、吸收剂隔片(有时称为固体电解质)和负极,其中电极中的至少一个或吸收剂隔片,最好是两个电极以及吸收剂隔片包含本发明的偏氟乙烯聚合物,且其中本发明电极的偏氟乙烯聚合物与电极材料结合在一起,本发明吸收剂隔片的偏氟乙烯聚合物与电解质材料结合在一起。 The electrochemical cell of the present invention is based on the operation of the positive electrode adjoin each other, the absorbent separator (sometimes referred to as a solid electrolyte) and a negative electrode, wherein the at least one separator or absorber electrode, preferably two electrodes and absorber the separator of the present invention comprising a vinylidene fluoride polymer, and wherein the electrode of the present invention, a vinylidene fluoride polymer bonded together with the electrode material, the present invention is an absorbent separator vinylidene fluoride polymer bonded together with the electrolyte material. 为了以本领域熟知的方法来提高组合元件的电压和/或电流强度,在电池结构中可采用多个电极和吸收剂隔片元件。 In order to methods known in the art to increase the voltage and / or current intensity of the combined elements, the plurality of electrodes may be employed and the absorbent element separator in the cell structure.

本发明的偏氟乙烯聚合物不需要有开孔或闭孔的结构来便于操作。 Vinylidene fluoride polymers according to the present invention does not require open or closed cell structure to facilitate the operation. 不论它最初处于多孔或无孔的状态,它均提供了增强的电解质迁移性和聚合物内部离子导电效果。 Whether it is initially in a state of porous or nonporous, which offer enhanced internal ion-conductive polymer and the effect of the electrolyte migration. 以前认为,在多孔聚合物孔表面与电极或电解质材料结合的偏氟乙烯电极或隔片吸收剂使得活性材料(无论是电极材料还是电解质材料)更有效地使用,并提供了制备有效的电极和隔片吸收剂结构的简便制造方法。 Previously thought, in the vinylidene fluoride electrode cellular polymer electrolyte material or the electrode surface and the binding or spacer such that the active absorber material (either the electrode material or electrolyte material) more efficient use and it provides an effective electrode and preparation simple method of manufacturing a spacer of the absorbent structure. 然而,对于本发明的聚偏氟乙烯聚合物,采用多孔聚合物的结构还有其它优点。 However, according to the present invention, the poly vinylidene fluoride polymers used as well as other advantages of the structure of the porous polymer.

也认为,活性材料在活性孔表面分离将便于改变吸收剂隔片或电极中粘合剂的用量来提高强度,而对电池性能的影响却很小。 Also believes, will facilitate the separation of the active material, a separator or an electrode to change the absorber in an amount to increase the strength of the binder in the active surface of the hole, and the effect on cell performance is very small. 因此用这种方法制得的电化学电池有改进的机械性能,并可制成自承式(self-supporting),即不需要用辅助的增强结构(如金属或其它常规的电池外壳材料)。 May therefore be made by this process of an electrochemical cell has improved mechanical properties, and can be made self-supporting (self-supporting), i.e., does not require auxiliary reinforcement structure (such as a metal or other conventional battery casing material).

这也使得制造容易,其中电化学电池被包封或包埋在与多孔电极和/或吸收剂隔片结构粘合的偏氟乙烯均聚物中。 This also makes it easy to manufacture, wherein the electrochemical cell is encapsulated or embedded in the porous polyvinylidene fluoride electrodes and / or the spacer structure bonded absorbent homopolymer. 通过简单的加热粘合或射频焊接或其它本领域熟知的类似方法可实现粘合。 By simple heat bonding or rf welding or other similar methods known in the art may be implemented adhesive. 不需要用粘合剂,但重要的是,电化学电池的外部(即包封物)应与和电极及吸收剂隔片的材料相同或大致相同,并更相容更有粘合性,从而简化生产,降低生产成本,因为与其它常规的干电池或二次电池结构相比,该电池的结构元件只采用了一种材料。 No need to use an adhesive, it is important that the outside of the electrochemical cell (i.e., encapsulant) should be the same and an electrode separator and absorbent material or substantially the same, and more and more compatible with the adhesive, thereby simplify production, reduce production costs, as compared with other conventional dry cell or secondary cell structures, structural elements of the cell using only one material.

聚偏氟乙烯通常吸收射频,也可通过介电技术来加热。 Polyvinylidene fluoride typically absorb radio frequency, it can also be heated by dielectric techniques. 也可用加热枪在压力下来封合聚偏氟乙烯表面。 May also be used in heat gun down pressure sealing polyvinylidene fluoride surfaces. 在制造较大的聚偏氟乙烯结构中,也可采用焊条来热封合两片已制成的片材。 In the manufacture of larger polyvinylidene fluoride structures, it may also be employed to heat seal two electrode sheets has been made. 获得的接头的强度通常与所用的基材树脂一样。 Strength of the joint obtained with the usual base resin used. 由于聚偏氟乙烯聚合物是耐磨、有韧性、耐化学性的,因此它们可用于电池的内部和外部元件,如上所述,这些元件可通聚合物过不用粘合剂的热封合方法来组装。 Because polyvinylidene fluoride polymers are abrasion resistance, toughness, chemical resistance, and thus they can be used for internal and external components of the battery, as described above, a polymer heat-sealing these elements adhesive can pass through without to assemble.

通过选择本发明的偏氟乙烯用作电极和选择这些聚合物或常规的VDF聚合物用作非常柔软的或稍有刚性的覆盖层,可以制成本身也是柔性或稍有刚性的结构。 By choosing the present invention, vinylidene fluoride polymers used as the electrode and select these conventional VDF polymer or as soft or very slightly rigid covering layer itself may be made of a slightly flexible or rigid structure. 在这一方面,还可通过使偏氟乙烯均聚物或共聚物的交联来增强刚性,交联通常采用化学交联,但最好采用有一些附带脱氟化氢作用的高能辐射(如高能(约10-20兆拉德)电子束辐射)来交联。 In this regard, also by vinylidene fluoride homo- or copolymer cross-linked to increase the rigidity, crosslink usually chemically cross-linked, but there are preferably used high-energy radiation comes dehydrofluorination (e.g., high-energy ( about 10 to 20 Mrad) electron beam radiation) crosslinked. 一个潜在的益处是偏氟乙烯聚合物中非晶型区域的进一步稳定化作用(即抑制随时间的结晶),这是很重要的,因为认为电解质的离子导电主要在非晶型或开孔区域中发生的。 One potential benefit of a vinylidene fluoride polymer is further stabilization of the amorphous region (i.e., the inhibition of crystallization over time), it is very important, because the ion conducting electrolyte that is primarily amorphous or open regions in the occurring.

如上所述,偏氟乙烯聚合物通常对离子导电性的影响使得它们适于制造电化学电池。 As described above, a vinylidene fluoride polymer is typically Effect of ionic conductivity making them suitable for making an electrochemical cell.

由于在电化学电池中需要有带电物质迁移性,因此认为聚偏氟乙烯聚合物中的带电物质会迁移通过非晶相。 Since the electrochemical cells need to have mobility of charged species, it is considered that polyvinylidene fluoride polymer charged species will migrate through the amorphous phase. 本发明的偏氟乙烯聚合物被认为有增强的更稳定的非晶相,特别是HFP和CTFE共聚物,它们在共聚单体含量较低时为电导率等提供了这种优点,从而提供了与均聚物接近的溶解度和温度的优点。 Vinylidene fluoride polymers according to the present invention are believed to have increased the amorphous phase more stable, particularly HFP and CTFE copolymers, which provides this advantage and conductivity at low comonomer content, thereby providing advantages and homopolymers and close to the solubility temperature.

在摩擦电系列中,大多数聚合物使电子稳定化。 In the triboelectric series, most polymers stabilize electrons. 然而偏氟乙烯聚合物在使阳离子空穴稳定化方面是独特的,而且是该方面最有效的介质之一,这大概是由于高电负性的偕二氟碳基团造成的。 However, the vinylidene fluoride polymer is a cationic stabilization of the hole unique, and this aspect is one of the most effective media, presumably due to the high electronegativity of the group of gem-fluorocarbon caused.

在本文描述的锂离子电池的特殊例子(如摇椅式电池)中,锂离子的比电荷高和离子尺寸小会导致主体偏氟乙烯聚合物环境中特异的相互作用,考虑到可获得的不可极化的电负性偕二氟碳基团的程度。 Specific examples of the lithium ion battery described herein (e.g., rocking chair batteries), the high specific charge lithium ions and ions of small size of the body can cause a vinylidene fluoride polymer interactions specific environment, not taking into account the available electrode degree of electronegativity of bis fluorocarbon group.

由于电导率与聚偏氟乙烯聚合物的结晶性成反比,因此可以确定传统的含有约7-25%六氟丙烯的偏氟乙烯共聚物可不以机械性能为代价就能显著减少聚合物的结晶结构,这样就可获得可接受的聚合物的离子电导率效果。 Since the copolymer of vinylidene fluoride and polyvinylidene fluoride conductivity is inversely proportional to the crystalline ethylene polymer, it can be determined about 7-25% contain conventional hexafluoropropylene polymer may not be able to significantly reduce the cost of the mechanical properties of crystalline structure, can be obtained so that acceptable ionic conductivity effects of the polymer. 发明者发现,本发明的共聚单体含量在8%(重量)以下,更佳地在6%(重量)以下的偏氟乙烯聚合物提供了与上述常规VDF/HFP共聚物相同或比其更佳的优点。 The inventors found that, according to the present invention, the comonomer content 8% (by weight) or less, more preferably 6% (by weight) or less of vinylidene fluoride polymers provide the same above-described conventional VDF / HFP copolymer or more than good advantage of.

当在制造电极或吸收剂隔片中采用本发明的偏氟乙烯聚合物时,可采用增塑剂如有机碳酸酯(如碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯等)来将结晶结构的影响减少到最低,并促进离子导电。 When using the present invention in the manufacture of electrodes or absorber septum vinylidene fluoride polymers, plasticizers may be employed such as organic carbonates (e.g. ethylene carbonate, propylene carbonate, dimethyl carbonate, etc.) to the influence the crystal structure reduced to a minimum and promote ionic conductivity. 也可采用其它溶剂或增塑剂,其包括二乙氧基乙烷、碳酸二乙酯、二甲氧基乙烷、碳酸二丙酯及其混合物,尤其是两组分或三组分的混合物。 Other solvents or plasticizers may also be employed, including diethoxyethane, diethylcarbonate, dimethoxyethane, dipropyl carbonate and mixtures thereof, especially the two component or three-component mixture of .

同样,根据本发明,各种多孔或无孔结构,取决于它们的拉伸强度,可通过拉伸或施加拉伸力来进行机械取向,以提高聚合物结构中的β构象量,从而可根据电解质和聚偏氟乙烯组成来提高离子电导率。 Also, according to the present invention, various porous or non-porous structures, depending on their tensile strength, tensile force is applied by stretching or by mechanically oriented, to increase the amount of β conformation of the polymer structure, so as to be in accordance with electrolyte and polyvinylidene fluoride composition to improve ion conductivity.

采用溶剂和非溶剂的组合将本发明的聚偏氟乙烯聚合物浇铸成薄的膜。 The solvent and non-solvent using a combination of polyvinylidene fluoride of the present invention will ethylene polymer cast into a thin film. 该方法在Benzinger等的美国专利No.4,384,074中有所描述,该文的内容结合入本文作为参考。 This method is described in U.S. Patent No.4,384,074 Benzinger and the like, the text of which is incorporated herein by reference. 本文所述的电极材料或电解质材料可在将聚偏氟乙烯溶液浇铸成薄膜或片材前掺入溶液中,随后,如果需要,可以将溶液转变成与电解质材料或电极结合的多孔性聚偏氟乙烯膜。 Herein electrolyte material or the electrode material may be polyvinylidene fluoride solution prior to casting as a film or sheet incorporated into a solution, followed by, if necessary, the solution may be converted to a porous polyvinylidene combined with electrode or electrolyte material fluoride film. 这些有或没有电极或电解质材料的薄膜或片材可以约为0.25-100密耳厚,特别是约0.5-10密耳厚,更特别是约1-8密耳厚,而且尤其适于用拉伸或施加拉伸力来进一步处理,以促进实现聚偏氟乙烯中铁电性能所需的β构象。 Those with or without electrodes or electrolyte material film or sheet may be about 0.25 to 100 mils thick, especially from about 0.5 to 10 mils thick, more particularly from about 1-8 mils thick, and is particularly suitable for use pull extension or tensile force is applied to further processing, in order to contribute to the desired polyvinylidene fluoride ferroelectric properties ethylene β conformation.

有三类有机液体可用来制备偏氟乙烯聚合物的溶液或分散体。 There are three classes of organic liquids can be used to prepare ethylene polymers of vinylidene fluoride solution or dispersion. 活性溶剂是那些在室温下溶解或溶胀偏氟乙烯聚合物的有机液体,其通常包括低级烷基酮、酯和酰胺组成。 Active solvents are those dissolved at room temperature or swell vinylidene fluoride polymer is an organic liquid, which typically include lower alkyl ketones, esters and amides. 潜溶剂是那些在室温下不溶解偏氟乙烯均聚物或共聚物的有机液体,然而它可在升高的温度下可溶解聚偏氟乙烯,它通常是中等链长度的烷基酮、酯、乙二醇醚和有机碳酸酯。 Latent solvents are those which do not dissolve vinylidene fluoride homopolymer or copolymer of an organic liquid at room temperature, but it can be dissolved at an elevated temperature, polyvinylidene fluoride, it is usually medium-chain length alkyl ketones, esters , glycol ethers and organic carbonates. 非溶剂是在高达液体沸点或偏氟乙烯聚合物的晶体熔点中首先能满足的温度下不能溶解或溶胀偏氟乙烯聚合物的有机液体。 Is a non-solvent does not dissolve at a temperature up to the crystalline melting point of the ethylene polymer of vinylidene fluoride or a liquid having a boiling point in the first to meet the vinylidene fluoride polymer or swellable organic liquids. 这些液体通常是芳烃、脂族烃和氯化烃或其它氯化的有机液体。 These liquids typically are aromatic hydrocarbons, aliphatic hydrocarbons and chlorinated hydrocarbons or other chlorinated organic liquids. 在制备本发明的聚偏氟乙烯聚合物膜或片材中采用溶剂和潜溶剂。 The solvent and cosolvent employed in the ethylene polymer film or sheet of poly-vinylidene fluoride in the present invention.

这些有机液体的离子列在下表A中。 These organic ionic liquids are listed in Table A below.

表A制备PVDF溶液或分散体的液体 Table preparing a liquid solution or dispersion of PVDF A

任何给出的液体的适用性根据PVDF树脂的确切类型和品级来决定。 The suitability of any given liquid is determined depending on the exact PVDF resin type and grade.

已经研究出其它方法来制备开孔泡沫多孔聚偏氟乙烯聚合物(在需要的时候),聚合物配方中含有化学或物理发泡剂,如吸收的二氧化碳。 A porous open-cell foam prepared polyvinylidene fluoride polymer (when necessary), the polymer formulation contains a chemical or physical blowing agent, such as carbon dioxide absorbed by other methods have been developed. 在制备电化学电池时最好采用物理发泡剂,因为泡沫结构中微量的化学发泡剂会对电池性能产生不利影响。 In the preparation of an electrochemical cell employed is preferably a physical blowing agent, because the adverse effects of trace chemical structural foam blowing agents have cell performance. 当采用二氧化碳或类似的物理发泡剂时,它们在超临界压力下被掺入聚偏氟乙烯中,然后通过热处理使制得的制品发泡。 When a physical blowing agent of carbon dioxide or the like, which are incorporated into the polyvinylidene fluoride at super critical pressure, by heat treatment and then foamed article obtained. 用这种方法制得的各种厚度的开孔膜有优良的机械完整性,与比重约为1.76-1.78的固体聚偏氟乙烯相比,它的比重约为1。 Apertured films of various thicknesses made available by this method has excellent mechanical integrity, and the solid specific gravity of about 1.76-1.78 polyvinylidene fluoride compared to its specific gravity of about 1.

同样,可通过加热非溶剂浆料中或是压力下对置平板间的粉末,直至各个颗粒相互充分熔融流动形成所需的开孔结构,将聚偏氟乙烯粉末烧结成多孔结构。 Similarly, the desired open cell structure may be formed by heating under pressure the non-solvent slurry, or the powder between the plates is set, until the individual particles sufficiently melt flow to each other, the polyvinylidene fluoride powder is sintered to form a porous structure. 也可采用如Menassen等在"A Polymer Chemist′s View on Fuel Cell Electrodes",Proceeding of the 34th International Power Source Symposium,June 25-28,1990,pp.408-10中所述的其它本领域已知的将聚合物粉末(如PTFE)烧结成开孔的多孔结构的方法。 May also be employed as Menassen et al "A Polymer Chemist's View on Fuel Cell Electrodes", Proceeding of the 34th International Power Source Symposium, June 25-28,1990, other art-known in the pp.408-10 the polymer powder (e.g., PTFE) porous sintered structure opening.

通过如Benzinger等在美国专利4,383,047中所述的将本发明的提供聚亚乙烯基的聚合物从溶剂和非溶剂的混合物中浇铸制得多孔膜,该膜在从浇铸溶液中成形后的厚度约为10密耳,它可用来制造电化学电池。 The pores of the membrane by Benzinger et al in U.S. Patent No. 4,383,047 of the present invention will provide a polymer polyvinylidene from a mixture of solvent and nonsolvent in the casting made much, thickness of the film after formation from the casting solution is about 10 mils, which can be used to manufacture electrochemical cells. 聚合物包含下述实施例1中的共聚物。 Polymer comprises a copolymer of embodiment 1 in the following Example. 该膜这样用于制造固体电解质的吸收剂-隔片:制备LiPF6在碳酸亚乙酯和碳酸亚丙酯为1∶1的混合物中的溶液,溶液加热至约125℃,将多孔共聚物膜浸在溶液中直至它与膜结合。 The film thus producing a solid electrolyte absorber - separator: Preparation of LiPF6 in ethylene carbonate and propylene carbonate in 1 mixture solution was heated to about 125 deg.] C, the porous copolymer film immersed until it is combined with the membrane in a solution.

同样,用同一多孔共聚物可制得正极。 Similarly, using the same porous copolymer can be obtained a positive electrode. 将膜浸泡在LiMn2O4、SS碳黑和LiPF6在碳酸亚乙酯和碳酸亚丙酯为1∶1的混合物的分散液和四氢呋喃中使其与多孔膜结合,使悬浮液在振动烧杯中搅拌以使固体物质保持悬浮直至与膜充分结合。 The membrane was immersed in LiMn2O4, SS carbon black and LiPF6 in ethylene carbonate and propylene carbonate dispersion liquid 1:1 mixture of tetrahydrofuran and allowed to bind to the porous membrane, the suspension was stirred in a beaker so that the vibration the solid material kept in suspension until adequately combined with the film. 然后将膜放在铝箔上。 The membrane was then placed on an aluminum foil.

负极的制备为,用制备正极所用的方法来制备石油焦炭、SS碳黑和LiPF6在1∶1碳酸亚乙酯和碳酸亚丙酯溶液中的分散液或悬浮液,在使悬浮液与多孔膜结合后将铜箔放在膜上。 Preparation of the negative electrode is, petroleum coke is prepared by the method used in preparing the positive electrode, SS carbon black and LiPF6 in 1:1 ethylene carbonate and propylene carbonate solution, dispersion or suspension in the suspension with the porous membrane after binding of the copper foil placed on the film.

电极和吸收剂-隔片或固体电解质中各种组分的比例与Gozdz等在美国专利No.5,296,318中的实施例1和8所述的基本相同。 And the absorbent electrode - separator or a solid electrolyte in the proportion of the various components and the like Gozdz in U.S. Patent No.5,296,318 Example 1 and 8 is substantially the same.

电极和电解质也可通过形成电极或电解质材料与聚偏氟乙烯粉末的干混物来从烧结的聚偏氟乙烯制得。 Electrode and the electrolyte may also be formed by an electrode or electrolyte materials with powdered polyvinylidene fluoride blend of dry ethylene vinylidene fluoride to be prepared from sintered polyethylene. 可采用已有技术中已知的干混技术,如转鼓式混合。 Known in the prior art may be employed in the dry blending techniques such as mixing drum rotation. 例如,可对聚偏氟乙烯粉末和电极或电解质材料的混合物进行滚筒磨或球磨一定时间,以充分保证获得良好的混合。 For example, roller mill or a ball mill may be a certain time of the mixture of polyvinylidene fluoride powder and the electrode or the electrolyte material, in order to sufficiently ensure good mixing. 可采用钢或其它金属容器或陶瓷容器,尤其是任一衬有聚偏氟乙烯或PTFE层的容器。 It can be steel or other metal containers or ceramic vessel, in particular any lined with a polyvinylidene fluoride or PTFE layer on the container. 在球磨情况下,也可采用涂覆有聚偏氟乙烯或PTFE层的钢或其它金属或陶瓷磨球。 In the case of milling, it may also be coated with a polyvinylidene fluoride or PTFE layer of steel or other metal or ceramic balls. 采用聚偏氟乙烯或PTFE涂层来基本消除引入系统的杂质或将其减少到最低。 Polyvinylidene fluoride or PTFE coating is introduced into the system to substantially eliminate or reduce impurities to a minimum. 如这里所述的通过施加热和压力将研磨后的混合物成形成电极和电解质。 As described herein by applying heat and pressure to form a milled mixture electrode and the electrolyte.

本领域技术人员应当理解本发明第一方面的无孔VDF/HFP共聚物或本发明的其它多孔或无孔偏氟乙烯聚合物可代替实施例1中的VDF/HFP来制成类似的电池。 Those skilled in the art will appreciate a first aspect of the present invention, a non-porous VDF / HFP copolymer, or other porous or non-porous polyvinylidene fluoride of the present invention polymers may be made in place of a similar battery. 1 Example VDF / HFP embodiment.

用于电极或电解质中的溶剂,如碳酸亚乙酯和碳酸亚丙酯及其等价物,尤其如本文所述的包括它们的混合物,可通过将电极和电解质结构浸泡在这些溶剂中来随后加入。 An electrode or electrolyte solvent, such as ethylene carbonate and propylene carbonate, and their equivalents, in particular as described herein including mixtures thereof, can be obtained by soaking the electrodes and electrolyte structures in such solvents is then added to. 浸泡可在室温或室温以上的温度下进行以使这些材料溶剂化效果最大并在电极或电解质中产生最优离子电导率。 May be soaked in the solvent effect of these materials and to produce an optimal maximum conductivity in the electrode or the electrolyte ions at a temperature of room temperature or above.

然后将这样制得的正极和负极放在上述制得的吸收剂隔片的相对面上,使铜和铝表面朝外,制成如图4所示的电池,其中铜膜14沿负极16的一个表面延伸,负极16在操作上与和电解质结合的吸收剂-隔片18毗连。 Then the thus obtained positive and negative electrodes on opposite sides of the above prepared absorbent obtained spacer, copper and aluminum surfaces facing outward, made battery shown in FIG. 4, in which the copper film 14 of the anode 16 a surface extends, the negative electrode 16 and the electrolyte in combination with the absorbent on the operating --18 contiguous septum. 铝膜22与正极20接触,而正极20与吸收剂隔片18的另一个表面接触,所有的元件在操作上均相互毗连。 22 positive electrode 20 in contact with aluminum, while the other surface of the positive electrode 20 into contact with the absorbent separator 18, all of the elements are adjacent to each other in operation. 聚偏氟乙烯均聚物的包封物12将电池完全包裹。 Polyvinylidene fluoride homopolymer encapsulates the battery 12 is fully wrapped. 包封物12可以是单层膜或是多层膜,如两层或三层膜,并沿所有侧面延伸并完全包覆电池10。 Encapsulant 12 may be a single layer film or a multilayer film, such as two or three-layer film, and extends along all sides of the battery 10 and completely coated. 铜和铝的导线(未显示)穿过包封物12,分别与膜14和22电接触,并与一载荷(未显示)连接形成电路。 Copper and aluminum wire (not shown) pass through the encapsulant 12, are in contact with the dielectric film 14 and 22, and is connected to a load (not shown) to form a circuit.

本文所述的摇椅式电池用的其它电解质也可用来代替LiPF6盐,用LiNiO2或LiCoO2材料代替前面例子中的LiMn2O4。 Other electrolytes described herein rocking chair battery can also be used in place of LiPF6 salt, instead of the previous example with LiMn2O4 LiNiO2 or LiCoO2 materials. 另外在制造负极时可用石墨而不是石油焦炭,但是石油焦炭是尤其佳的。 Also useful in the manufacture of a negative electrode of graphite rather than petroleum coke, it is and especially in the petroleum coke.

本发明的偏氟乙烯聚合物也可用于有锂有机电解质的电池中用作特殊电极活性材料的粘合剂、聚合物电池用的固体电解质、多孔网支撑的准固态凝胶电解质和作为电池基材。 Quasi-solid gel electrolyte vinylidene fluoride polymer of the present invention may also be used with a lithium organic electrolyte battery used as a binder specific electrode active material, polymer solid electrolyte battery, and a porous mesh supporting a battery-yl material.

本文所述的本发明偏氟乙烯聚合物也可用于锂/卤氧化物电池用作电池底部绝缘物。 The present invention is described herein vinylidene fluoride polymers may also be used in lithium / oxyhalide cells as a bottom cell insulation. 它们也可用于溴化锌电池中用作双极性电极的粘合剂或用于镍-金属氢化物电池中用作氢化物电极或镍电极的粘合剂。 Adhesive metal hydride battery or a nickel hydride electrode is used as electrode, - an adhesive or they can be used for nickel-zinc bromide battery as bipolar electrode.

本发明的偏氟乙烯聚合物也适于银-锌电池中用作锌电极的粘合剂,或在铅-酸电池中用作电极间的隔片和隔离物。 Vinylidene fluoride polymers according to the present invention are also suitable silver - zinc battery, the zinc electrode is used as a binder, or a lead - as a separator between the electrodes and the separator in the battery acid. 偏氟乙烯聚合物也可用于热电池中用作负极活性材料。 Vinylidene fluoride polymers may also be used in thermal batteries for use as a negative electrode active material. 除镍-金属氢化物电池外,偏氟乙烯聚合物也可用于其它碱性电池如镍-镉电池、锌-空气电池,尤其在采用缓冲电解质来抵消这些电池中的碱性介质的脱卤化氢作用。 In addition to a nickel - metal hydride battery, the vinylidene fluoride polymer may also be used in other alkaline batteries such as nickel - cadmium battery, zinc - air cells, particularly in the electrolyte using a buffer to counteract the dehydrohalogenation in alkaline medium of these cells in effect.

下列实施例进一步描述了发明者考虑采用的实施本发明的最佳模式,应当理解,这些实施例是说明性的,而没有限制性。 The following examples further describe the best mode embodiment of the present invention, the inventors considered, it should be understood that these examples are illustrative and not restrictive.

熔体粘度测定根据ASTM D3835在232℃和100S-1下进行。 The melt viscosity is performed at 232 deg.] C and 100S-1 according to ASTM D3835.

热性质根据ASTM D3418用差示扫描量热法(DSC)来测定。 Thermal properties were determined by differential scanning calorimetry (DSC) used by ASTM D3418.

HFP含量根据信号测定(signal assignment)和Pianca等在Polymer,vol.28,224-230(1987年2月)中描述的方法用19F NMR来测定。 HFP content in Polymer, method described in (February 1987) is determined using vol.28,224-230 19F NMR measurement based on a signal (signal assignment) Pianca and the like. 采用376.3MHz下的Unity 400分光计。 Using Unity 400 spectrometer at 376.3MHz. NMR谱可通过在50℃的氘化二甲基甲酰胺中用8.0微秒的激发脉冲宽度和10秒的循环延迟、在80℃的氘化二甲基亚砜中用6.0微秒的激发脉冲宽度和5秒的循环延迟、或50℃的氘化丙酮中用8.0微秒的激发脉冲宽度和20秒的循环延迟来获得。 NMR spectrum excited by 8.0 microsecond pulse width and cycle delay of 10 seconds in deuterated dimethylformamide deg.] C to 50 with, in deuterated dimethyl sulfoxide to 80 deg.] C with excitation pulses of 6.0 microseconds width and cyclic delay of five seconds, or deuterated acetone of 50 deg.] C with excitation cycle and a pulse width of 8.0 microseconds delay of 20 seconds is obtained.

分子量用尺寸排阻色谱法(SEC)来测定。 The molecular weight was determined by size exclusion chromatography (SEC). 在105℃的操作温度下,采用有一套PL凝胶2根混合B型柱、珠粒大小为10微米的Waters 150C色谱仪。 At the operating temperature of 105 ℃, using a set of two PL gel Mixed B type columns, 10 micron bead size Waters 150C chromatograph. 用HPLC级二甲基亚砜(DMSO)作为流速为1.0毫升/分钟的洗脱剂。 With HPLC grade dimethylsulfoxide (DMSO) as the flow rate of 1.0 ml / min eluent. 试样通过在100℃下DMSO中溶解5小时,然后过滤来制得。 Sample DMSO by dissolving 5 hours at 100 ℃, filtered then be prepared.

实施例1在7.5升不锈钢反应器中加入4.799kg去离子水、0.230kg全氟烷羧酸盐混合物的1%(重量)溶液和0.004kg石蜡。 Example 1 was added 4.799kg of 7.5 liter stainless steel reactor of deionized water, 0.230kg 1% of a perfluoroalkyl carboxylic acid salt mixture (by weight) solution of 0.004kg paraffin. 混合物用氮气吹扫并搅拌30分钟。 The mixture was purged with nitrogen and stirred for 30 minutes. 密封反应器并加热至80℃。 The reactor was sealed and heated to 80 ℃. 在反应器中加入0.355kg偏氟乙烯、0.049kg六氟丙烯(偏氟乙烯/六氟丙烯之比为88/12)和0.120kg的5%(重量)乙酸乙酯在去离子水中的溶液。 Reactor was added 0.355kg vinylidene fluoride, 0.049kg hexafluoropropylene (ratio of ethylene vinylidene fluoride / hexafluoropropylene of 88/12) was 0.120kg and 5% (wt.) Acetate in deionized water. 反应条件稳定在80℃和4480kPa下,然后加入0.026kg引发剂乳液来引发聚合反应,引发剂乳液由2%(重量)过氧二碳酸二正丙酯和0.15%(重量)分散在去离子水中的混合全氟烷羧酸盐组成。 The reaction conditions stabilized at 80 deg.] C and 4480kPa, then the emulsion was added 0.026kg initiator to initiate the polymerization reaction, the initiator emulsion is from 2% (by weight) of di-n-propyl peroxydicarbonate and 0.15% (by weight) was dispersed in deionized water mixed perfluoroalkyl carboxylates. 加入引发剂乳液使压力升高至4550kPa。 Initiator emulsion was added to raise the pressure 4550kPa. 以0.112kg/小时的速度加入引发剂乳液,以维持聚合反应,加入偏氟乙烯/六氟丙烯比为95/5的偏氟乙烯/六氟丙烯混合物来维持压力。 At 0.112kg / hr initiator emulsion was added at a rate to maintain the polymerization, vinylidene fluoride / hexafluoropropylene ratio of vinylidene fluoride / hexafluoropropylene 95/5 mixture to maintain pressure. 在4.2小时后,反应器中总共加入1.890kg偏氟乙烯和0.140kg六氟丙烯。 After 4.2 hours, the reactor was added a total of 0.140kg 1.890kg vinylidene fluoride and hexafluoropropylene. 停止所有的进料并冷却反应器。 Stopping all feeds the reactor was cooled. 冷却5分钟后,将搅拌速度降低78%,并放空残余的气体。 After cooling for 5 minutes, stirring speed was reduced 78%, and the residual gas is vented. 停止搅拌,进一步冷却反应器,然后倒出胶乳。 Stirring was stopped, the reactor is further cooled, and then poured latex. 聚合物树脂可这样分离获得:凝结胶乳、用沸水清洗获得的固体,并在110℃下干燥固体以得到细粉末。 The thus separated polymer resin may be obtained: The latex is coagulated, washed with boiling water to obtain solid, and the solid was dried at 110 deg.] C to give a fine powder. 这样制得的树脂的熔体粘度为2770Pa·s,DSC熔点为152℃,经NMR测得六氟丙烯含量为5.4%(重量)。 Thus obtained resin melt viscosity of 2770Pa · s, DSC melting point of 152 ℃, as measured by NMR hexafluoropropylene content (by weight) 5.4%.

实施例2在7.5升不锈钢反应器中加入4.913kg去离子水、0.230kg全氟烷羧酸盐混合物的1%(重量)溶液和0.004kg石蜡。 Example 2 was added 4.913kg of 7.5 liter stainless steel reactor of deionized water, 0.230kg 1% of a perfluoroalkyl carboxylic acid salt mixture (by weight) solution of 0.004kg paraffin. 混合物用氮气吹扫并搅拌30分钟。 The mixture was purged with nitrogen and stirred for 30 minutes. 密封反应器并加热至80℃。 The reactor was sealed and heated to 80 ℃. 在反应器中加入0.415kg偏氟乙烯、0.215kg六氟丙烯(偏氟乙烯/六氟丙烯之比为66/34)和0.010kg乙酸乙酯。 Reactor was added 0.415kg vinylidene fluoride, 0.215kg hexafluoropropylene (vinylidene fluoride / hexafluoropropylene ratio of 66/34 to) and ethyl acetate 0.010kg. 压力为4895kPa。 Pressure 4895kPa. 反应条件稳定在80℃下,然后加入0.040kg引发剂乳液来引发聚合反应,引发剂乳液由2%(重量)过氧二碳酸二正丙酯和0.15%(重量)分散在去离子水中的混合的全氟烷羧酸盐组成。 The reaction conditions stabilized at 80 ℃, mixed 0.040kg initiator to initiate emulsion polymerization, initiator emulsion from 2% (by weight) of di-n-propyl peroxydicarbonate and 0.15% (by weight) was dispersed in deionized water and then added perfluoroalkyl carboxylates. 压力在引发时降低,然后稳定在4825kPa。 Reducing the pressure in the initiation, then stabilized at 4825kPa. 以0.176kg/小时的速度加入引发剂乳液以维持聚合反应,加入偏氟乙烯/六氟丙烯比为84/16的偏氟乙烯/六氟丙烯混合物来维持压力。 At 0.176kg / hr initiator emulsion was added at a rate to maintain the polymerization, vinylidene fluoride / hexafluoropropylene ratio of vinylidene fluoride / hexafluoropropylene 84/16 mixture to maintain pressure. 在2.2小时后,反应器中总共加入1.585kg偏氟乙烯和0.445kg六氟丙烯。 After 2.2 hours, the reactor was added a total of 0.445kg 1.585kg vinylidene fluoride and hexafluoropropylene. 停止单体进料,维持引发剂乳液进料和80℃20分钟,消耗残余的单体。 The monomer feed is stopped, to maintain the emulsion feed and initiator 80 ℃ 20 minutes, and residual monomer was consumed. 停止引发剂进料和搅拌,使反应器稳定10分钟。 Stop stirring and initiator feed, the reactor was stable for 10 minutes. 将反应器冷却至45℃,放空,然后倒出胶乳。 The reactor was cooled to 45 ℃, vented, and the latex was decanted. 聚合物树脂可这样分离获得:凝结胶乳、用沸水清洗获得的固体,并在80℃下干燥固体以得到细粉末。 The thus separated polymer resin may be obtained: The latex is coagulated, washing the obtained solid with boiling water, and the solid was dried at 80 deg.] C to give a fine powder. 这样制得的树脂的熔体粘度为1220Pa·s,DSC熔点为114℃,经NMR测得六氟丙烯含量为17.2%(重量)。 Thus obtained resin melt viscosity of 1220Pa · s, DSC melting point of 114 ℃, as measured by NMR hexafluoropropylene content (by weight) 17.2%.

实施例3(实施例1的对比实施例)在7.5升不锈钢反应器中加入4.799kg去离子水、0.230kg全氟烷羧酸盐混合物的1%(重量)溶液和0.004kg石蜡。 Example 3 (Comparative Example Example 1) was added 7.5-liter stainless steel reactor, 4.799kg deionised water, 0.230kg 1% of a perfluoroalkyl carboxylic acid salt mixture (by weight) solution of 0.004kg paraffin. 混合物用氮气吹扫并搅拌30分钟。 The mixture was purged with nitrogen and stirred for 30 minutes. 密封反应器并加热至80℃。 The reactor was sealed and heated to 80 ℃. 在反应器中加入0.400kg偏氟乙烯、0.030kg六氟丙烯(偏氟乙烯/六氟丙烯之比为93/7)和0.120kg的5%(重量)乙酸乙酯在去离子水中的溶液。 Reactor was added 0.400kg vinylidene fluoride, 0.030kg hexafluoropropylene (ratio of ethylene vinylidene fluoride / hexafluoropropylene of 93/7) was 0.120kg and 5% (wt.) Acetate in deionized water. 反应条件稳定在80℃和4480kPa下,然后加入0.026kg引发剂乳液来引发聚合反应,引发剂乳液由2%(重量)过氧二碳酸二正丙酯和0.15%(重量)分散在去离子水中的混合的全氟烷羧酸盐组成。 The reaction conditions stabilized at 80 deg.] C and 4480kPa, then the emulsion was added 0.026kg initiator to initiate the polymerization reaction, the initiator emulsion is from 2% (by weight) of di-n-propyl peroxydicarbonate and 0.15% (by weight) was dispersed in deionized water perfluoroalkyl carboxylates mixed composition. 以0.112kg/小时的速度加入引发剂乳剂,以维持聚合反应,加入偏氟乙烯/六氟丙烯比为93/7的偏氟乙烯/六氟丙烯混合物来维持压力。 At 0.112kg / hr initiator emulsion was added to maintain the polymerization, vinylidene fluoride / hexafluoropropylene ratio of vinylidene fluoride / hexafluoropropylene 93/7 mixture to maintain pressure. 在3.1小时后,反应器中总共加入1.890kg偏氟乙烯和0.140kg六氟丙烯。 After 3.1 hours, the reactor was added a total of 0.140kg 1.890kg vinylidene fluoride and hexafluoropropylene. 停止单体进料,维持引发剂液剂进料和80℃20分钟,消耗残余单体。 The monomer feed is stopped, to maintain the liquid feed and the initiator 80 ℃ 20 minutes to consume residual monomers. 停止引发剂进料和搅拌,使反应器稳定10分钟。 Stop stirring and initiator feed, the reactor was stable for 10 minutes. 将反应器冷却至45℃,放空,然后倒出胶乳。 The reactor was cooled to 45 ℃, vented, and the latex was decanted. 聚合物树脂可这样分离获得:凝结胶乳,用沸水清洗获得的固体,并在110℃下干燥固体以得到细粉末。 The thus separated polymer resin may be obtained: The latex is coagulated, washed with boiling water to obtain solid, and the solid was dried at 110 deg.] C to give a fine powder. 这样制得的树脂的熔体粘度为2550Pa·s,DSC熔点为154℃,经NMR测得六氟丙烯含量为6.0%(重量)。 Thus obtained resin melt viscosity of 2550Pa · s, DSC melting point of 154 ℃, as measured by NMR hexafluoropropylene content (by weight) 6.0%.

实施例4在293升不锈钢反应器中加入200.0kg去离子水、1.00kg全氟烷羧酸盐混合物的10%(重量)溶液和0.015kg石蜡。 200.0kg Example 4 was added in 293-liter stainless steel reactor of deionized water, 1.00kg 10% of a perfluoroalkyl carboxylic acid salt mixture (by weight) solution of 0.015kg paraffin. 在加料时抽空反应器并加热至91℃,采用搅拌。 When the addition the reactor was evacuated and heated to 91 ℃, using stirring. 在反应器中加入12.6kg偏氟乙烯、0.8kg六氟丙烯(偏氟乙烯/六氟丙烯之比为94/6)和0.5kg乙酸乙酯,使得反应器压力升高至4480kPa。 In the reactor was charged 12.6kg vinylidene fluoride, hexafluoropropylene 0.8kg (vinylidene fluoride / hexafluoropropylene ratio of 94/6) and 0.5kg of ethyl acetate, so that the reactor pressure was raised to 4480kPa. 在加压时,当压力达到3445kPa时,开始加入引发剂乳液并维持在9.0kg/小时下直至引发剂乳液加入量为4.6kg,引发剂乳液由2%(重量)过氧二碳酸二正丙酯和0.15%(重量)分散在去离子水中的混合的全氟烷羧酸盐组成。 When the pressure, when the pressure reaches 3445kPa, start initiator emulsion was added and maintained at 9.0kg / hr until the initiator emulsion was added in an amount of 4.6kg, initiator emulsion consisting of 2% (by weight) of di-n-propyl mixed esters and perfluoroalkyl carboxylates 0.15% (by weight) was dispersed in deionized water composition. 进一步调节引发剂乳剂的加料速度以维持总单体进料速度为27.0kg/小时。 Further initiator feed rate adjusting agents to maintain the total monomer emulsion feed rate of 27.0kg / hr. 在反应器中加入偏氟乙烯和六氟丙烯比为94/6的单体混合物以维持压力在4480kPa下,直至反应器中总共加入85.3kg偏氟乙烯和5.4kg六氟丙烯。 Was added vinylidene fluoride and hexafluoropropylene ratio in the reactor of the monomer mixture 94/6 to maintain the pressure at 4480kPa, until the reactor was added a total of 85.3kg 5.4kg of vinylidene fluoride and hexafluoropropylene. 停止所有的进料,通过在91℃下搅拌20分钟然后在91℃下35分钟来消耗残余单体。 Stopping all feeds, stirring at 91 ℃ 20 minutes and then at 91 ℃ 35 minutes to consume residual monomers. 冷却反应器,放空并倒出胶乳。 The reactor was cooled, vented and the latex was decanted. 聚合物树脂可这样分离获得:凝结胶乳、用水清洗获得的固体,并干燥固体以得到细粉末。 Thus separated polymer resin may be obtained: solids latex is coagulated, washed with water to obtain, and the solid was dried to give a fine powder. 这样制得的树脂的熔体粘度为1740Pa·s,DSC熔点为155℃,经NMR测得六氟丙烯含量为4.7%(重量)。 Thus obtained resin melt viscosity of 1740Pa · s, DSC melting point of 155 ℃, as measured by NMR hexafluoropropylene content (by weight) 4.7%.

实施例5-12实施例5-8的共聚物用共聚物实施例1或2的方法制得,实施例9-12的共聚物用共聚物实施例3或4的方法制得,它们列在表1中。 Copolymer of Example 5-125-8 method of Example 1 or 2, the copolymer obtained embodiment, the method of Example 3 or 4 of the copolymer obtained in Example 9-12 Copolymer embodiment, they are listed in in FIG. 1.

表1试验数据实施例 1 2 5 6 7 8 3 4 9 10 11 12与该实施例相同的详述实施例 - - 1 1 1 2 - - 3 3 4 3温度,℃ 80 80 80 80 80 80 80 91 80 80 91 80压力,kPa 4550 4825 4550 4480 4480 4480 4480 4480 4480 4515 4480 4480初始加料[a]水,kg 4.799 4.913 4.837 4.768 4.797 4.723 4.799 200.0 4.837 4.768 200.0 4.723VDF,kg 0.355 0.415 0.365 0.365 0.460 0.400 0.400 12.6 0.390 0.365 11.0 0.455HFP,kg 0.049 0.215 0.030 0.129 0.163 0.207 0.030 0.8 0.017 0.060 1.9 0.128EtoAc溶液,kg 0.120 - 0.080 0.160 0.130 0.200 0.120 - 0.080 0.160 - 0.200EtoAc,kg - 0.010 - - - - - 0.5 - - 0.7 -NPP乳液,kg DETAILED DESCRIPTION Example 125,678,349,101,112 same as the test data in Example Table 1 Example of embodiment - - 1 1 1 2 - -. 4. 3. 3 3 Temperature, ℃ 80 80 80 80 80 80 80 9180809180 pressure, kPa 4550 4825 4550 4480 4480 4480 4480 4480 4480 4515 4480 4480 initial charge [a] water, kg 4.799 4.913 4.837 4.768 4.797 4.723 4.799 200.0 4.837 4.768 200.0 4.723VDF, kg 0.355 0.415 0.365 0.365 0.460 0.400 0.400 12.6 0.390 0.365 11.0 0.455HFP, kg 0.049 0.215 0.030 0.129 0.163 0.207 0.030 0.8 0.017 0.060 1.9 0.128EtoAc solution, kg 0.120 - 0.080 0.160 0.130 0.200 0.120 - 0.080 0.160 - 0.200EtoAc, kg - 0.010 - - - - - 0.5 - - 0.7 -NPP emulsion, kg 0.026 0.040 0.026 0.033 0.036 0.040 0.026 4.6 0.026 0.033 3.7 0.040总量VDF,kg 1.890 1.585 1.915 1.745 1.700 1.590 1.890 85.3 1.945 1.745 77.1 1.585HFP,kg 0.140 0.445 0.083 0.285 0.331 0.441 0.140 5.4 0.085 0.285 13.6 0.445NPP乳液,kg 0.506 0.460 0.413 0.422 0.352 0.463 0.405 8.5 0.540 0.491 8.3 0.563熔体粘度,Pa·s 2770 1220 3120 1660 1760 480 2550 1740 2240 1010 660 850熔点, 152 114 156 132 125 116 154 155 159 141 139 126聚合物k HFP,%(重量) 5.4 17.2 3.4 12.5 14.8 17.0 5.8 4.6 4.9 11.8 11.7 18.1[a]实施例5-12中的全氟烷羧酸盐溶液、全氟烷羧酸盐、石蜡和石蜡油与详述实施例的相同。 0.026 0.040 0.026 0.033 0.036 0.040 0.026 0.040 4.6 0.026 0.033 3.7 total VDF, kg 1.890 1.585 1.915 1.745 1.700 1.590 1.890 85.3 1.945 1.745 77.1 1.585HFP, kg 0.140 0.445 0.083 0.285 0.331 0.441 0.140 5.4 0.085 0.285 13.6 0.445NPP emulsion, kg 0.506 0.460 0.413 0.422 0.352 0.463 0.405 8.5 0.540 0.491 8.3 0.563 melt viscosity, Pa · s 2770 1220 3120 1660 1760 480 2550 1740 2240 1010 660 850 mp 152 114 156,132,125,116,154 155,159,141,139,126 polymer k HFP,% ( by weight) 5.4 17.2 3.4 12.5 14.8 17.0 5.8 4.6 4.9 11.8 11.7 18.1 [a] embodiment perfluoroalkyl carboxylate solution of Example 5-12, perfluoroalkyl carboxylates, paraffins and paraffin oils described in detail with the same embodiment .

本申请说明书和权利要求所用的术语“有改进透明性和流动性的溶液”是指本发明的含特定HFP标称含量的任何特定共聚物的溶液,当它溶解在列出的任何溶剂中的浓度与提供类似表Ⅱ中实施例12的描述性溶液性质的共聚物的浓度(共聚物有大致相同的特定HFP标称含量,用已有技术中详细描述的典型方法制得)相同时,它有类似表Ⅱ中实施例2所示的那些描述性性质。 The present specification and claims, the term "improved transparency and flowability of the solution" refers to any solution of the specific copolymer containing specific HFP nominal content of the present invention means, when it is dissolved in any solvent listed the concentration of the copolymer to provide similar concentrations described in table ⅱ solution properties of Example 12 (copolymer have substantially the same nominal HFP content of specific, exemplary methods using prior art have described in detail) are the same, it those described in Example 2 of similar properties shown in table ⅱ embodiment.

实施例溶液性质的评价表Ⅱ显示了实施例2和12的溶液性质。 Example embodiments of the solution properties evaluation table shows Ⅱ solution properties of Examples 2 and 12. 制得有所示重量百分比的混合物,需要时可采用加热来完全溶解聚合物和形成透明的溶液。 There are shown in percentages by weight was obtained mixture was heated to completely dissolve the polymer employed and form a clear solution if necessary. 然后使溶液冷却,在两周内每天进行观察。 The solution was then cooled and observed daily for two weeks. 共聚物2表现出胶凝趋势减少,且比共聚物12透明。 2 exhibit reduced gelation tendency copolymers, copolymers and transparent than 12. 共聚物2流动性和透明性的保留在依赖聚合物溶液的应用中(如浇铸膜的制备)是有利的。 Copolymer 2 Reserved flowability and transparency in the polymer solution in the application-dependent (e.g., cast film preparation) is advantageous.

表ⅡA中进一步显示了本发明的共聚物的胶凝趋势减少。 Table further shows the gel ⅡA trend copolymer of the present invention reduces. 表中显示了一些实施例的碳酸亚丙酯溶液的胶凝时间。 The table shows the gel time propylene carbonate solution of some embodiments. 用Rheometrics动态应力流变仪DSR-200来测定聚合物在碳酸亚丙酯(碳酸亚丙酯的标称纯度为99.7%)的20%(重量)溶液中的胶凝时间。 Rheometrics by dynamic stress rheometer DSR-200 polymeric gelling time was measured (by weight) solution in 20% propylene carbonate (nominal purity propylene carbonate 99.7%) of. 流变仪上装有Peltier固定装置(fixture)和溶剂阱(trap)。 Peltier with fixing means (fixtures) and a solvent trap (Trap) on the rheometer. 采用间隔为1mm的40mm平行板几何结构。 Intervals using 40mm parallel plate geometry of 1mm. 在测定当天使固体共聚物在室温下与碳酸亚丙酯混合,密封容器,通过在设定在120℃的Pierce Reacti-ThermHeating/StirringModule中加热并搅拌密封容器中的混合物1.0小时,制得溶液。 A solid copolymer angel when measured at room temperature with mixing propylene carbonate, sealed container, the sealed container in the mixture by heating at 120 deg.] C is set Pierce Reacti-ThermHeating / StirringModule and stirred for 1.0 hours to prepare solution. 在溶解结束时迅速将溶液加入预先设定在100℃的测试固定装置中。 At the end the solution is added rapidly dissolved in the test fixture previously set in 100 ℃. 当固定装置温度重新在100℃平衡时,立即以1Hz的动态振荡模式进行迅速冷却;重新平衡通常需要1分钟或更短。 When the fixing device temperature rebalancing 100 ℃, rapid cooling immediately dynamic oscillation mode of 1Hz; rebalancing typically requires 1 minute or less. 迅速冷却是以30℃/分钟的速度从100℃冷却到15℃。 Rapidly cooled at a speed of 30 ℃ / min cooling from 100 deg.] C to 15 ℃. 当达到15℃时,进行1分钟的平衡,然后开始时间扫描测定。 Upon reaching 15 ℃, for 1 min equilibration, and then scan the measurement start time. 在以1弧度/秒的速度进行时间扫描测定时,使试样保温在15℃。 When the scanning time measured at 1 rad / sec, the sample was incubated at 15 ℃. 继续时间扫描直至达到胶凝点。 Continue until the time to scan the gel point. 胶凝点取溶液储能模量G′和损耗模量G″相等的时间点。胶凝时间取开始扫描至到达胶凝点的时间。 The gel point was taken equal to the storage modulus G 'and loss modulus G "point in time. Gel time taken to start the scan time reaches the gel point.

图3中显示了HFP含量和20%(重量)碳酸亚丙酯溶液的胶凝时间对数值之间的关系。 Figure 3 shows the content of HFP and 20% (by weight) propylene carbonate solution of a gelling time relationship between the numerical value. 可以看出,在所有HFP含量范围内,本发明共聚物的胶凝时间比已有技术制得的共聚物的胶凝时间长。 As can be seen, in all the range of the content of HFP, copolymer of the present invention, the gelling time is longer than the prior art gel time of the resulting copolymer. 本发明共聚物的胶凝趋势的减少在将这些溶液加工成浇铸膜以及其它溶液应用中是有利的。 Reduce the gelling tendency of the copolymers of the invention are advantageous in the processing of these solutions into a solution cast film as well as other applications.

表Ⅱ溶液性质聚合物浓度和溶剂[a] 外观实施例2 实施例1210%在MEK中 流体,透明 流体,透明20%在MEK中 流体,透明 第2天略有疏松的凝胶,透明30%在MEK中 1第4天有一些凝胶,透明 1天后略有疏松的凝胶,浑浊;第4天有凝胶,浑浊10%在MPK中 流体,透明 流体,透明20%在MPK中 流体,透明 2小时后有一些凝胶,透明;1天后有凝胶,稍浑浊10%在MiBK中 流体,透明 第4天有凝胶,透明10%在CPO中 流体,透明 流体,透明10%在CHO中 流体,透明 流体,透明20%在CHO中 第2天有一些凝胶,透明 1天后有一些凝胶,透明;第2天有一些凝胶,浑浊10%在EtoAC中 流体,透明 第7天有一些凝胶,透明20%在EtoAC中 流体,透 TABLE Ⅱ solution properties of polymer concentration and solvent [a] Appearance Example 2 Example 1,210% in MEK fluid, transparent liquid, transparent fluid 20% in MEK, day 2 slightly loose transparent gels, transparent cases 30% 1 in MEK some day 4 gel, a transparent gel after 1 day somewhat loose, turbidity; day 4 gel, 10% MPK cloudy fluid, transparent liquid, transparent fluid 20% MPK, after 2 hours, some transparent gel, a transparent; gel after 1 day, 10% MiBK slightly turbid fluid, transparent gel day 4, the fluid in the CPO 10% transparent, the transparent fluid, transparent 10% CHO fluid, transparent liquid, transparent 20% on day 2 in CHO some gel, 1 day some transparent gel, a transparent; 2 days some gel, turbid fluid EtoAC 10%, the transparent day 7 Some gel, 20% transparent fluid in EtoAC, the transflective 1天后流体,浑浊;第3天有一些凝胶,浑浊10%在n-PrOAc中 流体,透明 流体,透明10%在i-PrOAc中 流体,透明 第6天有一些凝胶,透明10%在EGMEA中 流体,透明 第6天有凝胶,透明10%在DMC中 流体,透明 第7天有一些凝胶,透明20%在DMC中 流体,透明 1天后有一些凝胶,浑浊;第2天有大量凝胶,浑浊20%在混合物2中 流体,透明 第14天,流体,浑浊[a]聚合物浓度用%(重量)表示,除非另有所指。 1 day fluid turbidity; some gel 3 days, the turbidity of 10% n-PrOAc in the fluid, transparent liquid, transparent 10% i-PrOAc in the fluid, there are the transparent gel 6 days, 10% transparent fluid EGMEA, 6 days a transparent gel, 10% DMC transparent fluid, there are the transparent gel day 7, 20% DMC transparent fluid, there are the transparent gel after 1 day, cloudy; day 2 there are a large number of gel, 20% in the mixture cloudy fluid, transparent 2 day 14, fluid turbidity [a] a polymer concentration expressed in% (wt), unless otherwise indicated. MEK是丁酮,MPK是甲基丙基酮,MiBK是甲基异丙基酮,CPO是环戊酮,CHO是环己酮,EtOAc是乙酸乙酯,N-PrOAc是乙酸正丙酯,i-PrOAc是乙酸异丙酯,EGMEA是乙二醇单甲基醚乙酸酯,DMC是碳酸二甲酯,混合物2由35.4重量份MiBK、29.8重量份CHO和30重量份DMC组成。 MEK is methyl ethyl ketone, MPK methyl propyl ketone, MiBK methyl isopropyl ketone, CPO is cyclopentanone, CHO is cyclohexanone, EtOAc is ethyl acetate, N-PrOAc is n-propyl acetate, i -PrOAc isopropyl acetate, ethylene glycol monomethyl ether is EGMEA acetate, dimethyl carbonate DMC, a mixture of 35.4 parts by weight of 2 MiBK, CHO and 29.8 parts by weight 30 parts by weight of DMC composition.

表ⅡA溶液胶凝时间[a]实施例编号 胶凝时间1 4251 5123 3423 3946 4,9136 8,3226 12,92410 93410 1,55310 3,1912 77,0002 62,40012 14,10012 47,500[a]在15℃下碳酸亚丙酯中的20%(重量)溶液。 Table ⅡA gel time was [a] Gel time Example No. 1 4251 5123 3423 3946 4,9136 8,3226 12,92410 93410 1,55310 3,1912 77,0002 62,40012 14,10012 47,500 [a] in propylene carbonate 20% (by weight) solution at 15 ℃. 胶凝时间以秒表示。 Gel time in seconds.

薄膜光泽度和透明性的评价用溶液性质测试中的一些不胶凝的溶液来制备薄膜,以测试光泽度和透明性。 Evaluation of glossiness and transparency of the film to prepare a film with a test solution properties Some ungelled solution to test gloss and transparency. 用间隙为250微米的0.127米刮涂机将膜浇铸在Leneta Form 2A不透明图表上。 Using a knife coater gap of 0.127 m to 250 micron film was cast on Leneta Form 2A opacity chart. 使浇铸膜在室温下干燥3天。 That the cast film was dried at room temperature for 3 days. 用HunterLab Progloss PG-2光泽度计来测定薄膜光泽度,结果列在表Ⅲ中。 With HunterLab Progloss PG-2 gloss meter film gloss was measured, the results shown in Table Ⅲ. 用HunterLab Labscan 2比色计测定不透明图表的黑色部分上的薄膜的白度指数(whiteness index)(CIELAB L*值),来测得薄膜雾度,测定结果示于表Ⅳ。 Whiteness index (whiteness index) (CIELAB L * value) of a thin film on the black portion of an opacity chart measured with HunterLab Labscan 2 colorimeter to the measured haze of the film, measurement results are shown in Table IV. 共聚物2制得的膜表现出可用更广范围的溶剂获得比用共聚物12制得的膜更高的光泽度。 Copolymer 2 obtained film exhibits a wider range of solvents that may be obtained with a higher degree of luster than 12 copolymer prepared film. 从共聚物2和12制得的膜的雾度大致相同,但是共聚物2制得的膜的一些例子中观察到有显著低的雾度。 Substantially the same as the haze and the obtained copolymer 2 film 12 made of, but some examples of the copolymer 2 obtained film was observed a significantly lower haze. 这些结果结合在一起,表明本发明的VDF/HFP共聚物更能用于高光泽度、高透明度的膜应用中。 These results together, the present invention show VDF / HFP copolymer film for better application of high gloss, high transparency of.

表Ⅲ浇铸膜的光泽度聚合物浓度和溶剂[a] 光泽度,20/60实施例2 实施例1220%在MEK中 33.6/69.0 31.3/68.710%在MPK中 31.4/68.9 1.3/18.710%在CPO中 0.7/16.9 2.0/27.710%在EtOAc中 29.4/66.6 29.4/68.010%在n-PrOAc中 31.9/70.1 16.0/57.010%在i-PrOAc中 31.6/69.4 15.4/56.210%在DMC中 35.4/70.6 30.1/68.620%在混合物2中 34.6/71.2 0.1/2.4[a]聚合物浓度和溶剂标明%(重量)和烧铸,膜所用的溶剂。 Table Ⅲ cast film gloss polymer concentration and solvent [a] gloss, 20/60 Example 2 Example 1,220% in MEK 33.6 / 69.0 31.3 / 31.4 68.710% in MPK / 68.9 1.3 / CPO at 18.710% 0.7 / 16.9 2.0 / 27.710% in EtOAc 29.4 / 66.6 29.4 / 68.010% in n-PrOAc 31.9 / 70.1 16.0 / 57.010% in i-PrOAc 31.6 / 69.4 15.4 / 56.210 percent in the DMC 35.4 / 70.6 30.1 / 68.620% in the mixture 2 34.6 / 71.2 0.1 / 2.4 [a]% polymer concentration and solvent indicated solvent (by weight) and burning casting, membrane used. MEK是丁酮,MPK是甲基丙基酮,CPO是环戊酮,EtOAc是乙酸乙酯,n-PrOAc是乙酸正丙酯,i-PrOAc是乙酸异丙酯,DMC是碳酸二甲酯,混合物2由35.4重量份丁酮、29.8重量份环己酮和30重量份DMC组成。 MEK is methyl ethyl ketone, methyl propyl ketone MPK, the CPO is cyclopentanone, EtOAc is ethyl acetate, n-PrOAc is n-propyl acetate, i-PrOAc isopropyl acetate, the DMC dimethyl carbonate, 35.4 parts by weight of a mixture of 2-butanone, 29.8 parts by weight of cyclohexanone and 30 parts by weight of DMC composition.

表Ⅳ浇铸膜的透明性聚合物浓度和溶剂[a] 透明性,CIELAB L*[b]实施例2 实施例1220%在MEK中 6.59 6.2210%在MPK中 6.19 14.4810%在CPO中 15.18 15.5610%在EtOAc中 7.38 5.8410%在n-PrOAc中 5.64 7.3410%在i-PrOAc中 5.61 7.7910%在DMC中 6.21 5.7320%在混合物2中 5.36 17.85[a]聚合物浓度和溶剂标明%(重量)和浇铸,膜所用的溶剂。 Example 2 Table transparent polymer concentration and solvent cast film Ⅳ [a] of transparency, CIELAB L * [b] Embodiment 1220% 6.19 6.59 6.2210% 14.4810% 15.5610% at 15.18 in the CPO in MEK MPK in the in EtOAc 7.38 5.8410% 5.64 7.3410% 5.61 7.7910% 6.21 5.7320%% (wt.) and casting, in 5.36 17.85 [a] and the polymer concentration in the solvent mixture was indicated in the n-PrOAc in i-PrOAc membrane DMC solvent used. MEK是丁酮,MPK是甲基丙基酮,CPO是环戊酮,EtOAc是乙酸乙酯,n-PrOAc是乙酸正丙酯,i-PrOAc是乙酸异丙酯,DMC是碳酸二甲酯,混合物2由35.4重量份丁酮、29.8重量份环己酮和30重量份DMC组成。 MEK is methyl ethyl ketone, methyl propyl ketone MPK, the CPO is cyclopentanone, EtOAc is ethyl acetate, n-PrOAc is n-propyl acetate, i-PrOAc isopropyl acetate, the DMC dimethyl carbonate, 35.4 parts by weight of a mixture of 2-butanone, 29.8 parts by weight of cyclohexanone and 30 parts by weight of DMC composition.

[b]雾度标准:L*<7 不起雾7<L*<9 起雾非常少9<L*<11 稍稍起雾11<L*<15 中度起雾15<L*严重起雾实施例热性能的评价最终熔点是半结晶聚合物的使用和加工中的重要参数。 [B] Haze Standard: L * <7 non-fogging 7 <L * <9 very little fogging 9 <L * <11 slightly fogging 11 <L * <15 Moderate fogging 15 <L * serious fogging evaluation of thermal properties of final melting point Example is an important embodiment and the processing parameters used in the semi-crystalline polymer. 已知VDF/HFP共聚物的最终熔点与共聚物中的HFP含量有关。 Known VDF / HFP copolymers with HFP content of the copolymer final melting point of about. VDF/HFP共聚物实施例的HFP含量和最终熔点之间的关系如图1所示。 HFP content and the relationship between the melting point of the final embodiments VDF / HFP copolymer as shown in FIG. 可以看到,本发明的共聚物和用已有技术详细描述的合成方法制得的共聚物落在不同的熔点曲线上,这表明它们是不同的物质,在给定的HFP含量下,已有技术共聚物的熔点较高。 Can be seen, the copolymers of the invention and prior art synthetic method described in detail using the obtained copolymer falls on different melting curves, suggesting that they are different substances, at a given HFP content, has higher melting copolymer technology. 本发明共聚物的熔点较低的性质可以允许采用比已有技术合成的共聚物更低的加工温度。 The lower melting point nature of the invention allows the use of the copolymer may be a copolymer of lower than the prior art synthesis process temperature.

在碳酸二甲酯中的可萃取物的评价一般步骤将1克聚合物和9克碳酸二甲酯放在25ml密闭容器中。 The extract was evaluated in the dimethyl carbonate may be general procedure 1 gram of polymer and 9 g of dimethyl carbonate in 25ml sealed container. 在用适当方法维持所需温度24小时的同时,用适当的方法连续搅拌容器中的物质。 At the same time by a suitable means of maintaining a desired temperature for 24 hours, the material in the vessel was stirred continuously by a suitable method. 然后将容器中所有的物质转移到离心管中并离心分离得到不溶解的聚合物。 The vessel was then all of the material was transferred to a centrifuge tube and centrifuged to obtain a polymer insoluble. 将液相转移至合适的配衡容器中并蒸发溶剂。 The liquid phase was transferred to a suitable tared container and the solvent was evaporated. 对容器中的残余物称重,并以%(重量)可萃取物记录。 Of residue weighed container, and in% (by weight) extractables record.

在40℃下测定萃取至碳酸二甲酯中的聚合物量。 Determination of the amount of polymer extracted into dimethyl carbonate at 40 ℃. 数据示于表Ⅴ。 Data are shown in Table Ⅴ. 用已有技术中详细描述的合成方法制得的共聚物用“N”作标记。 Copolymers prepared by prior art synthesis methods described in detail obtained with "N" mark. 用本发明所述方法制得的共聚物用“U”作标记。 Copolymers prepared by the method of the present invention, a "U" mark.

表ⅤHFP含量、分子量和组成分布的均匀性对聚合物在DMC中的溶解度的影响 Effect Table ⅤHFP content, molecular weight distribution and uniformity of the composition of the solubility of the polymer in the DMC

粗略的测定结果表明,所有N样品萃取至碳酸二甲酯中的聚合物的量较高。 Coarse measurement results showed that all N samples extracted to a higher amount of the polymer of dimethyl carbonate. 图2显示了可萃取物对于HFP含量%(摩尔)的曲线。 Figure 2 shows curves extractables% for HFP content (mol). 对于两类材料可以绘出两条不同的曲线。 For the two different types of materials can be plotted curves. 上面一条曲线(N样品)表明,与U曲线相比,对于给定的HFP含量可萃取物的量明显较高。 An upper curve (N samples) showed that, as compared with the U-curve, for a given amount of extractables HFP content was significantly higher. 测得的这些曲线的斜率为:N聚合物为3%可萃取物/HFP%(摩尔),U聚合物为1.7%可萃取物/HFP%(摩尔)。 The slope of these curves measured as: N 3% polymer extractables / HFP% (mol), U polymer is 1.7% extractables / HFP% (mol).

在表Ⅵ和Ⅶ中显示了N聚合物和U聚合物在单函数和双函数模型下观察和计算出的%可萃取物。 Shows the observed and the calculated function in single and dual function model N% extractables in a polymer and a U polymer in Table Ⅵ and Ⅶ.

表Ⅵ作为HFP含量或HFP含量和Mn函数的N聚合物的%(重量)可萃取物的比较 As Table Ⅵ% N HFP content of the polymer and Mn or a function of HFP content (by weight) of the extract was comparable

</tables>(模型1)%(重量)可萃取物=2.9(HFP%(摩尔))-0.4(模型2)%(重量)可萃取物=46.4+1.7(HFP%(摩尔))-0.00028(Mn)表Ⅶ作为HFP含量或HFP含量和Mn函数的U聚合物的%(重量)可苯取物的比较 </ Tables> (Model 1)% (wt) extractables = 2.9 (HFP% (mole)) - 0.4 (Model 2)% (wt) extractables = 46.4 + 1.7 (HFP% (mole)) - 0.00028 comparison (Mn) as table ⅶ% U HFP content of the polymer and Mn or a function of HFP content (by weight) of the extract can be benzene

</tables>(模型1)%(重量)可萃取物=1.7(HFP%(摩尔))-3.2(模型2)%(重量)可萃取物=-1.2+1.5(HFP%(摩尔))-8×10-6(Mn)在说明书和所附的权利要求中,术语“可萃取物的重量百分数在用选自下式a)%(重量)可萃取物=1.7(HFP%(摩尔))-3.2b)%(重量)可萃取物=-1.2+1.5(HFP%(摩尔))-8×10-6(Mn)计算出的可萃取物重量百分数的1.5%范围内”指40℃下在碳酸二甲酯中的可萃取物的重量百分数测定值必须在用任一式计算出的特定聚合物的可萃取物数值的1.5%绝对误差内。 </ Tables> (Model 1)% (wt) extractables = 1.7 (HFP% (mole)) - 3.2 (Model 2)% (wt) extractables = -1.2 + 1.5 (HFP% (mole)) - 8 × 10-6 (Mn) in the specification and the appended claims, the term "extractables in weight percent selected from the following formulas a)% (wt) extractables = 1.7 (HFP% (mol)) -3.2b)% (wt) extractables = -1.2 + 1.5 (HFP% (mole)) - in the range of 8 × 10-6 (Mn) calculated weight percent extractables 1.5% "means at 40 ℃ weight percent extractables value measured in dimethyl carbonate must be 1.5% absolute error in the formula using the specific polymer according to any one of the calculated values ​​of extractables.

就是说,如果用式1或2计算出的可萃取物重量百分数为3.0,而观察值在1.5-4.5%之间,则它在预定的覆盖数值范围内。 That is, if the calculated Formula 1 or 2 may extract 3.0 weight percent, observed value between 1.5 to 4.5%, it is within a predetermined value range coverage. 同样,如果观察值为8.0%,则当从任一式计算出的数值在6.5-9.5%之间时,它也在预定的范围内。 Similarly, if the observed value of 8.0%, then when the calculated value from any of formula is between 6.5 to 9.5%, which is also a predetermined range.

实施例13-有基本均匀的单体分布的聚偏氟乙烯聚合物/三氟氯乙烯共聚物按照实施例1的步骤提供含有0.40kg偏氟乙烯和0.0124kg三氟氯乙烯(VDF/CTFE为97/3)的初始加料,用VDF/CTFE为96/4的连续加料和引发剂乳液来维持反应,总加料量适合于反应器的体积,VDF约为1.9525kg,CTFE为0.0775kg,获得CTFE含量为4.0%的标题共聚物。 Example 13 has a substantially uniform distribution of monomers in the polymer polyvinylidene fluoride / chlorotrifluoroethylene copolymer The procedure of Example 1 to provide 0.40kg comprising vinylidene fluoride and chlorotrifluoroethylene 0.0124kg (VDF / CTFE of 97/3) of the initial charge, with VDF / CTFE and initiator is continuously fed to maintain the reaction emulsion 96/4, the total applied quantity is adapted to the volume of the reactor, of VDF about 1.9525kg, CTFE is 0.0775kg, CTFE to obtain content of 4.0% of the title copolymer.

在上述用来测定碳酸二甲酯中的可萃取物的方法中,在室温下以1500rpm离心30分钟,以使溶液和不溶物分离,在机械泵真空下在50℃下干燥70小时,以测定分离得到的溶液中固体的重量。 In the above method for determination of dimethyl carbonate may be in the extract, at room temperature, centrifuged at 1500rpm 30 minutes to the solution and the insolubles were separated, at 50 deg.] C under a mechanical pump vacuum dried for 70 hours to determine the solid was isolated by weight obtained.

申请人特别指出并明确提出要求的本发明的主要内容在所附的权利要求书中。 Applicants specifically noted in the book and the main content of the present invention is clearly required in the appended claims.

Claims (10)

1. 1. 一种改进的电化学电池,电池有正极、吸收剂隔片和负极,其中至少一个电极和/或所述吸收剂隔片包含结合有电解质材料的偏氟乙烯聚合物,其中改进之处包括偏氟乙烯聚合物基本上由选自有双峰型分子量分布的偏氟乙烯均聚物、有基本均匀的单体分布的偏氟乙烯/三氟氯乙烯共聚物以及偏氟乙烯和六氟丙烯共聚物的偏氟乙烯聚合物组成,偏氟乙烯和六氟丙烯的共聚物含有最高为24%重量的六氟丙烯,其溶液有改善的透明性和流动性;对于最高含8%重量HFP标称含量的共聚物,它的可萃取物的重量百分数在通过选自下式a)%重量可萃取物=1.7(HFP%摩尔)-3.2b)%重量可萃取物=-1.2+1.5(HFP%摩尔)-8×10-6(Mn)式计算出的可萃取物重量百分数的±1.5%范围内,对于HFP标称含量大于8%重量的共聚物,其DSC熔点比用已有技术中详细描述的合成方法制得的HFP标称重量百分 An improved electrochemical cell, the battery has a positive electrode, a negative electrode and an absorbent separator, wherein the at least one electrode and / or the absorbent sheet comprises a spacer electrolyte material combined with vinylidene fluoride polymer, wherein the improvement comprises the partial fluoride polymer selected from vinylidene fluoride with a substantially bimodal molecular weight distribution homopolymer with a vinylidene fluoride / chlorotrifluoroethylene copolymer substantially uniform distribution of monomers, and vinylidene fluoride and hexafluoropropylene copolymer a copolymer of vinylidene fluoride polymer, a vinylidene fluoride and hexafluoropropylene containing up was 24% by weight of hexafluoropropylene, which was transparent and improved flowability; containing 8% by weight for the highest nominal HFP copolymer content, its weight percent in the extract can be selected by the following formulas a)% wt extractables = 1.7 (HFP% mol) -3.2b)% wt extractables = -1.2 + 1.5 (HFP% mol) in the range of ± 1.5% -8 × 10-6 (Mn) calculated by the equation extractables weight percent, for a nominal HFP content is greater than 8% by weight of the copolymer having a DSC melting point than with the prior art detail synthetic methods described obtained weight percent nominal HFP 相同的共聚物低至少2.5℃。 Same copolymer is at least 2.5 ℃.
2. 2. 根据权利要求1所述的电池,其中偏氟乙烯聚合物是有双峰型分子量分布的偏氟乙烯均聚物。 Is a vinylidene fluoride bimodal molecular weight distribution homopolymer battery according to claim 1, wherein the vinylidene fluoride polymer.
3. 3. 根据权利要求1所述的电池,其中偏氟乙烯聚合物是有最高为20%重量三氟氯乙烯且有基本均匀的单体分布的偏氟乙烯/三氟氯乙烯共聚物。 There are up to 20% by weight of chlorotrifluoroethylene and has a substantially uniform distribution of monomers vinylidene fluoride / chlorotrifluoroethylene copolymer battery according to claim 1, wherein the vinylidene fluoride polymer.
4. 4. 根据权利要求3所述的电池,其中VDF/CTFE共聚物含有高达8%重量的CTFE。 The battery according to claim 3, wherein the VDF / CTFE copolymer contains up to 8% by weight of CTFE.
5. 5. 根据权利要求4所述的电池,其中VDF/CTFE共聚物含有2-6%重量的CTFE。 The battery according to claim 4, wherein the VDF / CTFE copolymer contains 2-6% by weight of CTFE.
6. 6. 根据权利要求1所述的电池,其中聚偏氟乙烯聚合物是VDF/HFP共聚物。 The battery according to claim 1, wherein the polyvinylidene fluoride polymer is a VDF / HFP copolymer.
7. 7. 根据权利要求6所述的电池,其中VDF/HFP共聚物最高含有8%重量的HFP。 The battery according to claim 6, wherein VDF / HFP copolymer containing up to 8% by weight of HFP.
8. 8. 根据权利要求7所述的电池,其中VDF/HFP共聚物含有2-6%重量的HFP。 The battery according to claim 7, wherein VDF / HFP copolymer contains 2-6% by weight of HFP.
9. 9. 一种改进的电化学电池,电池有正极、吸收剂隔片和负极,其中至少一个电极和/或所述吸收剂隔片包含结合有电解质材料的偏氟乙烯聚合物,其中改进之处包括偏氟乙烯聚合物基本上由六氟丙烯最高含量为8%重量的VDF/HFP共聚物组成,该共聚物的可萃取物的重量百分数比在权利要求1中确定的式a或b计算出的可萃取物重量百分数的±1.5%范围内。 An improved electrochemical cell, the battery has a positive electrode, a negative electrode and an absorbent separator, wherein the at least one electrode and / or the absorbent sheet comprises a spacer electrolyte material combined with vinylidene fluoride polymer, wherein the improvement comprises the partial fluoride polymer consists essentially of the highest content of hexafluoropropylene is 8 wt% VDF / HFP copolymer, a or b in the formula 1 may be calculated to determine the weight of extractables percentage of the copolymer as claimed in claim ratio extract weight percent of the range of ± 1.5%.
10. 10. 根据权利要求9所述的电池,其中VDF/HFP共聚物中六氟丙烯的含量为2-6%重量。 The battery according to claim 9, wherein the content VDF / HFP copolymer of hexafluoropropylene 2-6% by weight.
CNB988002078A 1997-02-28 1998-02-27 Electrochemistry cell CN1311577C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US3834697P true 1997-02-28 1997-02-28
US3101598A true 1998-02-26 1998-02-26
PCT/US1998/004071 WO1998038687A1 (en) 1997-02-28 1998-02-27 Copolymers of vinylidene fluoride and hexafluoropropylene having reduced extractable content and improved solution clarity

Publications (2)

Publication Number Publication Date
CN1217824A true CN1217824A (en) 1999-05-26
CN1311577C CN1311577C (en) 2007-04-18

Family

ID=26706722

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB988002078A CN1311577C (en) 1997-02-28 1998-02-27 Electrochemistry cell

Country Status (8)

Country Link
EP (1) EP0907976A4 (en)
JP (1) JP2002513506A (en)
KR (1) KR100537303B1 (en)
CN (1) CN1311577C (en)
CA (1) CA2251648A1 (en)
HU (1) HU9903748A3 (en)
ID (1) ID20294A (en)
WO (1) WO1998038687A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100557866C (en) * 2004-06-09 2009-11-04 吉莱特公司 Electrochemical cells
CN101046503B (en) * 2006-03-29 2011-02-16 深圳市比克电池有限公司 Method for testing explosion cause of lithium ion cell explosion
CN104151754A (en) * 2014-08-15 2014-11-19 上海三爱富新材料股份有限公司 High-fluidity ethylene-tetrafluoroethylene copolymer composition and preparation method thereof
CN106898825A (en) * 2017-05-03 2017-06-27 苏州载物强劲新材料科技有限公司 A kind of bipolarity Zinc ion battery and preparation method thereof

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100444134B1 (en) 1997-12-26 2004-08-09 구레하 가가쿠 고교 가부시키가이샤 Polymer electrolyte and nonaqueous battery containing the same
US8303609B2 (en) 2000-09-29 2012-11-06 Cordis Corporation Coated medical devices
JP4092669B2 (en) * 1998-04-27 2008-05-28 ソニー株式会社 Solid electrolyte secondary battery
IT1307756B1 (en) * 1999-02-05 2001-11-19 Ausimont Spa Polymer electrolytes for rechargeable lithium batteries.
GB2346729B (en) * 1999-02-10 2003-01-15 Aea Technology Plc Polymer electrolyte
GB0018635D0 (en) * 2000-07-31 2000-09-13 Aea Technology Plc Polymer electrolyte
DE10104988A1 (en) * 2001-02-03 2002-08-08 Varta Geraetebatterie Gmbh Process for the production of electrode foils
WO2004019344A1 (en) * 2002-08-26 2004-03-04 Nippon Oil Corporation Ion conducting film
US7279174B2 (en) 2003-05-08 2007-10-09 Advanced Cardiovascular Systems, Inc. Stent coatings comprising hydrophilic additives
US7066970B2 (en) 2003-05-09 2006-06-27 The Gillette Company Electrochemical cells
US9114198B2 (en) 2003-11-19 2015-08-25 Advanced Cardiovascular Systems, Inc. Biologically beneficial coatings for implantable devices containing fluorinated polymers and methods for fabricating the same
USRE45744E1 (en) 2003-12-01 2015-10-13 Abbott Cardiovascular Systems Inc. Temperature controlled crimping
JP4815795B2 (en) * 2004-12-01 2011-11-16 ソニー株式会社 Lithium ion secondary battery

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093427A (en) * 1990-05-10 1992-03-03 Atochem North America, Inc. Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same
US5429891A (en) * 1993-03-05 1995-07-04 Bell Communications Research, Inc. Crosslinked hybrid electrolyte film and methods of making and using the same
US5296318A (en) * 1993-03-05 1994-03-22 Bell Communications Research, Inc. Rechargeable lithium intercalation battery with hybrid polymeric electrolyte
US5460904A (en) * 1993-08-23 1995-10-24 Bell Communications Research, Inc. Electrolyte activatable lithium-ion rechargeable battery cell
TW342537B (en) * 1995-03-03 1998-10-11 Atochem North America Elf Polymeric electrode, electrolyte, article of manufacture and composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100557866C (en) * 2004-06-09 2009-11-04 吉莱特公司 Electrochemical cells
CN101046503B (en) * 2006-03-29 2011-02-16 深圳市比克电池有限公司 Method for testing explosion cause of lithium ion cell explosion
CN104151754A (en) * 2014-08-15 2014-11-19 上海三爱富新材料股份有限公司 High-fluidity ethylene-tetrafluoroethylene copolymer composition and preparation method thereof
CN106898825A (en) * 2017-05-03 2017-06-27 苏州载物强劲新材料科技有限公司 A kind of bipolarity Zinc ion battery and preparation method thereof
CN106898825B (en) * 2017-05-03 2019-02-05 江苏强劲新能源科技有限公司 A kind of preparation method of bipolarity Zinc ion battery

Also Published As

Publication number Publication date
KR20000065176A (en) 2000-11-06
ID20294A (en) 1998-11-26
CN1311577C (en) 2007-04-18
HU9903748A2 (en) 2000-03-28
CA2251648A1 (en) 1998-09-03
HU9903748A3 (en) 2000-06-28
JP2002513506A (en) 2002-05-08
WO1998038687A1 (en) 1998-09-03
EP0907976A1 (en) 1999-04-14
EP0907976A4 (en) 2005-11-02
KR100537303B1 (en) 2006-07-14

Similar Documents

Publication Publication Date Title
EP0793287B1 (en) Polyvinylidene fluoride (PVdF) homopolymer as a solid polymer electrolyte in Lithium ion cells
US6143216A (en) Batteries with porous components
DE69637433T2 (en) Hybrid polymer compound electrolyte and non-acid electrochemical cell
US9202631B2 (en) Porous film and secondary battery electrode
US4339473A (en) Gamma radiation grafting process for preparing separator membranes for electrochemical cells
KR100559110B1 (en) Bis(perfluoroalkylsulfonyl)imide surfactant salts in electrochemical systems
US9799917B2 (en) Waterborne fluoropolymer composition
CN1186391C (en) Polymer gel electrolyte and lithium cell using same
EP0821423B1 (en) Water-repellency agent for cells and cells
US6387570B1 (en) Lithium secondary battery, polymer gel electrolyte and binder for use in lithium secondary batteries
TWI549334B (en) Separator for secondary battery with high heat resistance
US7736810B2 (en) Separators for winding-type lithium secondary batteries having gel-type polymer electrolytes and manufacturing method for the same
JP3675460B2 (en) Organic electrolyte and lithium battery using the same
RU2358358C1 (en) Improved safety electrode fabricated through cross-linked polymer injection and electrochemical device containing such electrode
TWI330902B (en)
JP2853096B2 (en) Rechargeable lithium insertion batteries using hybrid polymer electrolyte
JP5213443B2 (en) Polyolefin microporous membrane
US7931995B2 (en) Solid electrolyte composite for electrochemical reaction apparatus
US5418091A (en) Polymeric electrolytic cell separator membrane
US7217480B2 (en) Organic electrolytic solution and lithium battery using the same
KR100448083B1 (en) Solid electrolyte composite for electrochemical reaction apparatus
US20110165473A1 (en) Nonaqueous electrolyte solution secondary battery separator and nonaqueous electrolyte solution secondary battery using the same
US5429891A (en) Crosslinked hybrid electrolyte film and methods of making and using the same
JP4418140B2 (en) Polymer electrolyte, its manufacturing method, and lithium battery using the same
JP4050251B2 (en) Organic electrolyte and lithium battery using the same

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1020116

Country of ref document: HK

C14 Grant of patent or utility model
C17 Cessation of patent right